JP5763527B2 - Imidazole compound-containing microencapsulated composition, curable composition using the same, and masterbatch type curing agent - Google Patents

Description

  The present invention relates to an imidazole compound having a specific structure microencapsulated, a curable composition using the imidazole compound, and a masterbatch type curing agent.

  Epoxy resins have a wide range of paints, electrical and electronic insulating materials, and adhesives because their cured products are excellent in mechanical properties, electrical properties, thermal properties, chemical resistance, adhesiveness, etc. It is used for purposes. Currently, the epoxy resin composition that is generally used is a two-part epoxy resin composition that is used by mixing two parts of an epoxy resin and a curing agent at the time of use. The two-part epoxy resin composition can be cured at room temperature, but the epoxy resin and the curing agent are stored separately before use, and each compound is measured and mixed as needed immediately before use. It is. Furthermore, since curing proceeds immediately after mixing, the usable time as a composition is limited. Therefore, the blending frequency is increased, the working efficiency is lowered, and the effective use amount of the composition is limited.

  In order to solve the above-mentioned problems of the two-part epoxy resin composition, a one-part epoxy resin composition has been conventionally proposed. For example, a one-component epoxy resin composition in which a curing agent such as dicyandiamide, BF3-amine complex, or an amine salt is blended with an epoxy resin as a latent curing agent has been proposed.

  Patent Document 1 proposes that an imidazole compound having a specific structure having a urea bond or an amide bond in the molecule serves as an early curing agent or curing accelerator for epoxy resins. In Patent Document 2, 1- (2-aminoethyl) -2-methylimidazole and a compound having an isocyanate group are reacted in acetonitrile, and a white solid of an imidazole compound containing a urea bond obtained by precipitation is epoxyated. It has been proposed to be used as a curing agent for resins. In patent document 3, the hardening | curing agent for epoxy resins by which the surface was coat | covered with the reaction material of the isocyanate compound is proposed.

JP-A-64-66172 JP 2000-290260 A Japanese Patent Laid-Open No. 01-70523

  However, epoxy resin compositions using these curing agents do not have a sufficient balance between storage stability and curability. For example, since those having excellent storage stability have low curability, it is necessary to increase the temperature for curing or to cure for a long time. On the other hand, since a thing with high curability has low storage stability, it is necessary to store at low temperature, such as -20 degreeC. For example, an epoxy resin composition using a curing agent disclosed in Patent Documents 1 and 2 is not practical from the viewpoint of productivity because of poor storage stability. The epoxy resin composition using the curing agent disclosed in Patent Document 3 does not have sufficient storage stability in the presence of a solvent, particularly solvent stability in the presence of methyl ethyl ketone.

  In particular, in the field of electronic equipment in recent years, in order to cope with higher circuit density and improved connection reliability, to use materials with low heat resistance as lighter mobile devices, and to improve productivity , One-part epoxy resin compositions with excellent fast-curing properties at low temperatures, storage stability, and stability in the presence of solvents (solvent stability) and latent curing to achieve one-part epoxy resin compositions Agents are required. However, the one-pack type epoxy resin composition and latent curing agent that sufficiently satisfy these characteristics are not yet known.

  The present invention has been made in view of the above circumstances, and when used as a curing agent for an epoxy resin or the like, a composition having excellent low-temperature curability, high storage stability, and high solvent stability, The main object is to provide an epoxy resin curing agent and an epoxy resin composition using the same.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by microencapsulating an imidazole compound having a specific structure, and based on this finding, the present invention It came to make.

（式中、Ｒ^１、Ｒ^２、Ｒ^３は、各々独立して、水素原子、ハロゲン基、置換基を含んでもよい炭素数１〜２０のアルキル基、置換基を含んでもよい芳香族基、置換基を含んでもよい炭素数１〜２０のアルコキシ基、又は置換基を含んでもよいフェノキシ基を表す。Ｑは、置換基を含んでもよい炭素数１〜２０の２価の炭化水素を表す。ｍは、１〜１００の整数を表す。Ｚは、価数ｍを有する有機基を表す。Ｙは、下記式（Ｇ）で表される尿素結合、チオ尿素結合、アミド結合、又はチオアミド結合を表す。）

〔２〕
Ｒ^１、Ｒ^２、Ｒ^３が、各々独立して、水素原子、炭素数１〜１０のアルキル基、又は炭素数１〜１０のアルコキシ基であり、
Ｑが、炭素数１〜２０の２価の炭化水素であり、
ｍが、１〜３の整数である、〔１〕に記載のイミダゾール化合物含有マイクロカプセル化組成物。
〔３〕
Ｒ^１、Ｒ^２、Ｒ^３が、各々独立して、水素原子、炭素数１〜１０のアルキル基、又は炭素数１〜１０のアルコキシ基であり、
Ｑが、炭素数３〜２０の２価の炭化水素であり、
ｍが、１〜３の整数である、〔１〕に記載のイミダゾール化合物含有マイクロカプセル化組成物。
〔４〕
Ｙが、尿素結合である、〔３〕に記載のイミダゾール化合物含有マイクロカプセル化組成物。
〔５〕
前記イミダゾール化合物は、１０℃以上で固体であり、結晶性又は非晶性である、〔１〕〜〔４〕のいずれか一項に記載のイミダゾール化合物含有マイクロカプセル化組成物。
〔６〕
イミダゾール化合物は、２５℃以上で固体であり、かつ２５０℃以下で融点を有する結晶性固体である、〔１〕〜〔５〕のいずれか一項に記載のイミダゾール化合物含有マイクロカプセル化組成物。
〔７〕
前記イミダゾール化合物の最大粒径が１００μｍ以下であり、かつ
粒径が０．１μｍ以上１００μｍ以下である粒子が、前記イミダゾール化合物中に９０質量％以上含有される、〔１〕〜〔６〕のいずれか一項に記載のイミダゾール化合物含有マイクロカプセル化組成物。
〔８〕
前記コアが、前記イミダゾール化合物と低分子アミン化合物とを含有する、〔１〕〜〔７〕のいずれか一項に記載のイミダゾール化合物含有マイクロカプセル化組成物。
〔９〕
前記シェルが、イソシアネート化合物から誘導される有機高分子を主成分として含有し、かつ１６３０〜１６８０ｃｍ^−１の赤外線を吸収する結合基と１６８０〜１７２５ｃｍ^−１の赤外線を吸収する結合基とを表面に少なくとも有する、〔１〕〜〔８〕のいずれか一項に記載のイミダゾール化合物含有マイクロカプセル化組成物。
〔１０〕
前記シェルが、イソシアネート化合物から誘導される有機高分子を主成分として含有し、かつ１７３０〜１７５５ｃｍ^−１の赤外線を吸収する結合基を少なくとも有する、〔１〕〜〔９〕のいずれか一項に記載のイミダゾール化合物含有マイクロカプセル化組成物。
〔１１〕
前記コア１００質量部に対し、前記シェルが０．０１〜１００質量部である、〔１〕〜〔１０〕のいずれか一項に記載のイミダゾール化合物含有マイクロカプセル化組成物。
〔１２〕
〔１〕〜〔１１〕のいずれか一項に記載のイミダゾール化合物含有マイクロカプセル化組成物１００質量部に対して、エポキシ樹脂１０〜５０，０００質量部を含有する、硬化性組成物。
〔１３〕
〔１２〕に記載の硬化性組成物を主成分として含有する、マスターバッチ型硬化剤。
〔１４〕
〔１２〕に記載の硬化性組成物、又は〔１３〕に記載のマスターバッチ型硬化剤を含有する、ペースト状組成物。
〔１５〕
〔１２〕に記載の硬化性組成物、又は〔１３〕に記載のマスターバッチ型硬化剤を含有する、フィルム状組成物。
〔１６〕
〔１２〕に記載の硬化性組成物、又は〔１３〕に記載のマスターバッチ型硬化剤を含有する、接着剤。
〔１７〕
〔１２〕に記載の硬化性組成物、又は〔１３〕に記載のマスターバッチ型硬化剤を含有する、接合用ペースト。
〔１８〕
〔１２〕に記載の硬化性組成物、又は〔１３〕に記載のマスターバッチ型硬化剤を含有する、接合用フィルム。
〔１９〕
〔１２〕に記載の硬化性組成物、又は〔１３〕に記載のマスターバッチ型硬化剤を含有する、導電性材料。
〔２０〕
〔１２〕に記載の硬化性組成物、又は〔１３〕に記載のマスターバッチ型硬化剤を含有する、異方導電性材料。
〔２１〕
〔１２〕に記載の硬化性組成物、又は〔１３〕に記載のマスターバッチ型硬化剤を含有する、異方導電性フィルム。
〔２２〕
〔１２〕に記載の硬化性組成物、又は〔１３〕に記載のマスターバッチ型硬化剤を含有する、絶縁性材料。
〔２３〕
〔１２〕に記載の硬化性組成物、又は〔１３〕に記載のマスターバッチ型硬化剤を含有する、封止材料。
〔２４〕
〔１２〕に記載の硬化性組成物、又は〔１３〕に記載のマスターバッチ型硬化剤を含有する、コーティング用材料。
〔２５〕
〔１２〕に記載の硬化性組成物、又は〔１３〕に記載のマスターバッチ型硬化剤を含有する、塗料組成物。
〔２６〕
〔１２〕に記載の硬化性組成物、又は〔１３〕に記載のマスターバッチ型硬化剤を含有する、プリプレグ。
〔２７〕
〔１２〕に記載の硬化性組成物、又は〔１３〕に記載のマスターバッチ型硬化剤を含有する、熱伝導性材料。That is, the present invention is as follows.
[1]
A core containing an imidazole compound represented by the following formula (1);
A shell containing an organic polymer, an inorganic compound, or both, and covering the surface of the core;
A microencapsulated composition containing an imidazole compound.

(Wherein R ¹ , R ² and R ³ each independently represents a hydrogen atom, a halogen group, an alkyl group having 1 to 20 carbon atoms which may contain a substituent, an aromatic group which may contain a substituent, An alkoxy group having 1 to 20 carbon atoms which may contain a substituent, or a phenoxy group which may contain a substituent, Q represents a divalent hydrocarbon having 1 to 20 carbon atoms which may contain a substituent. m represents an integer of 1 to 100. Z represents an organic group having a valence m. Y represents a urea bond, a thiourea bond, an amide bond, or a thioamide bond represented by the following formula (G). Represents.)

[2]
R ¹ , R ² , and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms,
Q is a divalent hydrocarbon having 1 to 20 carbon atoms,
The imidazole compound-containing microencapsulated composition according to [1], wherein m is an integer of 1 to 3.
[3]
R ¹ , R ² , and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms,
Q is a divalent hydrocarbon having 3 to 20 carbon atoms,
The imidazole compound-containing microencapsulated composition according to [1], wherein m is an integer of 1 to 3.
[4]
The imidazole compound-containing microencapsulated composition according to [3], wherein Y is a urea bond.
[5]
The imidazole compound-containing microencapsulated composition according to any one of [1] to [4], wherein the imidazole compound is solid at 10 ° C. or higher and is crystalline or amorphous.
[6]
The imidazole compound-containing microencapsulated composition according to any one of [1] to [5], wherein the imidazole compound is a crystalline solid having a melting point of 25 ° C. or higher and a melting point of 250 ° C. or lower.
[7]
Any of [1] to [6], wherein the imidazole compound has a maximum particle size of 100 μm or less, and particles having a particle size of 0.1 μm or more and 100 μm or less are contained in the imidazole compound by 90% by mass or more. An imidazole compound-containing microencapsulated composition according to claim 1.
[8]
The imidazole compound-containing microencapsulated composition according to any one of [1] to [7], wherein the core contains the imidazole compound and a low molecular amine compound.
[9]
It said shell, and a bonding group that absorbs infrared bonding group and 1680～1725Cm ^-1 which contains an organic polymer derived from an isocyanate compound as a main component, and absorbs infrared 1630～1680Cm ^-1 to the surface The imidazole compound-containing microencapsulated composition according to any one of [1] to [8], at least.
[10]
Any one of [1] to [9], wherein the shell contains an organic polymer derived from an isocyanate compound as a main component and has at least a bonding group that absorbs infrared rays of 1730 to 1755 cm ^−1. The imidazole compound-containing microencapsulated composition.
[11]
The imidazole compound-containing microencapsulated composition according to any one of [1] to [10], wherein the shell is 0.01 to 100 parts by mass with respect to 100 parts by mass of the core.
[12]
The curable composition containing 10-50,000 mass parts of epoxy resins with respect to 100 mass parts of imidazole compound containing microencapsulated compositions as described in any one of [1]-[11].
[13]
A master batch type curing agent comprising the curable composition according to [12] as a main component.
[14]
A paste-like composition containing the curable composition according to [12] or the masterbatch type curing agent according to [13].
[15]
The curable composition as described in [12], or the film-form composition containing the masterbatch type hardening | curing agent as described in [13].
[16]
The adhesive containing the curable composition as described in [12], or the masterbatch type hardening | curing agent as described in [13].
[17]
A bonding paste containing the curable composition according to [12] or the masterbatch type curing agent according to [13].
[18]
A bonding film containing the curable composition according to [12] or the masterbatch type curing agent according to [13].
[19]
A conductive material containing the curable composition according to [12] or the masterbatch type curing agent according to [13].
[20]
An anisotropic conductive material containing the curable composition according to [12] or the masterbatch type curing agent according to [13].
[21]
An anisotropic conductive film containing the curable composition according to [12] or the masterbatch type curing agent according to [13].
[22]
The insulating material containing the curable composition as described in [12], or the masterbatch type hardening | curing agent as described in [13].
[23]
The sealing material containing the curable composition as described in [12], or the masterbatch type hardening | curing agent as described in [13].
[24]
The curable composition as described in [12], or the coating material containing the masterbatch type hardening | curing agent as described in [13].
[25]
The curable composition as described in [12], or the coating composition containing the masterbatch type hardening | curing agent as described in [13].
[26]
A prepreg containing the curable composition according to [12] or the masterbatch type curing agent according to [13].
[27]
The heat conductive material containing the curable composition as described in [12], or the masterbatch type hardening | curing agent as described in [13].

  According to the present invention, when used as a curing agent for an epoxy resin, the composition has excellent low-temperature curability, high storage stability, and also achieves high solvent stability, and curing for an epoxy resin using the composition An agent and an epoxy resin composition can be realized.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

  The imidazole compound-containing microencapsulated composition of the present embodiment includes a core containing an imidazole compound having a specific structure, an organic polymer, an inorganic compound, or both, and a shell covering the surface of the core. , Containing. The imidazole compound-containing microencapsulated composition of the present embodiment has a solid imidazole compound having a specific structure as a core agent, and the surface is coated with a shell. The imidazole compound-containing microencapsulated composition can be used as a curing agent for an epoxy resin, and further can be a master batch type curing agent in which the imidazole compound-containing microencapsulated composition is dispersed in an epoxy resin.

Hereinafter, the imidazole compound which is a core agent of this Embodiment is demonstrated.
The imidazole compound used in the present embodiment is represented by the following formula (1).

In the formula, each of R ¹ , R ² and R ³ independently represents a hydrogen atom, a hydroxyl group, a halogen group, an alkyl group having 1 to 20 carbon atoms which may contain a substituent, or an aromatic group which may contain a substituent. Represents a C1-C20 alkoxy group which may contain a substituent, or a phenoxy group which may contain a substituent.

  The halogen group represents fluorine, chlorine, bromine, or iodine.

  The hydrocarbon structure of an alkyl group or alkoxy group having 1 to 20 carbon atoms may be a straight chain structure or a branched structure, and may further be a structure containing an alicyclic group such as a cyclohexyl group. These hydrocarbon sites may contain a substituent within a range that does not affect the curing reaction, and examples of these substituents include a hydroxyl group, a halogen group, and a nitrile group.

  Examples of the aromatic group include a phenyl group, a naphthyl group, and a biphenyl group. The aromatic ring in the aromatic group and phenoxy group may contain a hydroxyl group, a halogen group, a nitrile group, an alkoxy group or the like as long as it does not affect the curing reaction.

In the imidazole compound used in the present embodiment, R ¹ is preferably hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aromatic group, or a phenoxy group. In particular, since hydrogen, an alkyl group, and an alkoxy group have an electron donating property, the charge density of tertiary nitrogen at the 3-position of the imidazole ring is improved, so that the reactivity is improved and the curing rate at low temperature is improved. In addition, when an alkyl group or alkoxyl group having more than 10 carbon atoms is used as a curing agent, for example, the adhesiveness of the obtained cured product tends to deteriorate. From the above viewpoint, R ¹ is more preferably hydrogen, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

R ² and R ³ are preferably hydrogen, an optionally substituted alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms, hydrogen, an alkyl group having 1 to 10 carbon atoms, Or a C1-C10 alkoxy group is more preferable. In particular, since hydrogen, an alkyl group, and an alkoxy group have an electron donating property, the charge density of tertiary nitrogen at the 3-position of the imidazole ring is improved, so that the reactivity is improved and the curing rate at low temperature is improved. Moreover, when it uses as a C10 or less alkyl group or alkoxy group, for example, when it uses as a hardening | curing agent, it exists in the tendency for the adhesiveness of the obtained hardened | cured material to improve further.

  In the above formula (1), Q is a C 1-20 divalent hydrocarbon group which may contain a substituent. The hydrocarbon group is a saturated hydrocarbon group, an unsaturated hydrocarbon group having a double bond inside, or an aromatic group that may have an aromatic ring. The hydrocarbon group may have a straight chain structure or a branched structure, and may have an alicyclic structure. Examples of the substituent include halogen groups such as fluorine, chlorine and bromine, acyl groups, amino groups, nitrile groups and hydroxyl groups.

  The number of carbon atoms in Q is preferably 3-20, more preferably 3-10, still more preferably 3-6, and even more preferably 3-4. When the carbon number of Q is 3 or more, the curing rate to an epoxy resin of 100 ° C. or less is further improved. For example, when particularly low temperature curability of about 140 ° C. is required, since the heating temperature is relatively high even if it is low temperature, the melting point of the imidazole compound of the present embodiment and the solubility in epoxy resin are different. However, there is no significant difference in the curing rate. However, regarding the curing rate at a lower temperature, the melting point of the imidazole compound is low, and if the solubility in the epoxy resin is high, the curing rate tends to increase. In order to achieve curing at a lower temperature, it is necessary to lower the melting point and improve the solubility in the epoxy resin. From this point of view, the present inventors have found that when the number of carbon atoms in Q is 3 or more in the present embodiment, the solubility in the epoxy resin is improved and the melting point of the imidazole compound of the present embodiment is lowered. I found it. According to this knowledge, the carbon number of Q is preferably 3 or more from the viewpoint that the curability at a lower temperature can be further improved. Moreover, when carbon number is below the said upper limit, it exists in the tendency for it to be excellent in low-temperature curability, and for adhesiveness to become still better.

  It is particularly preferable that Q has any structure represented by the following formula (2).

  Moreover, among the above, it is particularly preferable to have any structure represented by the following formula (2a) from the viewpoint of further excellent low-temperature curability.

  In the above formula (1), Y represents a urea bond, a thiourea bond, an amide bond, or a thioamide bond, and the nitrogen contained in each bond is bonded to Q in the formula. Y is preferably a urea bond or a thiourea bond. Among these, a urea bond is preferable from the viewpoint of further excellent low-temperature curability.

  M in the above formula (1) represents an integer of 1 to 100. 1-20 are preferable, as for m, 1-10 are more preferable, and 1-3 are still more preferable.

  Z in the above formula (1) is an organic group having a valence m. Examples of the organic group include a hydrocarbon group and an aromatic group, and a hetero atom such as oxygen, nitrogen, or phosphorus may be included in the structure.

  The imidazole compound used in the present embodiment is generally a compound containing an amino group-containing imidazole compound represented by the following formula (3) and an isocyanate group or isothiocyanate group represented by the following formula (4), or It can be obtained by reaction with a compound containing a carboxyl group or a carbodithioic acid group. The structure of Z in the above formula (1) is the same as Z in the following formula (4) which is a raw material to be used.

  The imidazole compound of this embodiment is solid at 10 ° C. or higher, and is preferably crystalline or amorphous. The crystalline solid means that an endothermic peak due to melting is observed when the temperature is raised at 10 ° C./min by differential thermal analysis. In the imidazole compound of the present embodiment, the melting point that is the peak top of the endothermic peak is 10 ° C. or higher. In the present embodiment, the above-mentioned solid state at 10 ° C. or more and non-crystalline means that when a metal sphere having a diameter of 9.55 mm and a weight of 3.5 g is placed on the compound surface for 48 hours, the compound surface The temperature at which the traces of the metal spheres remain is less than 10 ° C. When the imidazole compound is a solid that does not have fluidity at 10 ° C. or higher, it is efficient that the viscosity increases during the work of blending with the epoxy resin or until it is molded into a desired shape (for example, 1 day). Since it can suppress well, a high potential can be maintained as a latent curing agent.

  The imidazole compound used in this embodiment is solid at 25 ° C. or higher, more preferably crystalline, and further preferably a crystalline solid having a melting point of 25 ° C. or higher and 250 ° C. or lower. In the case of a crystalline solid having a melting point of 25 ° C. or higher, not only can a certain potential be maintained as described above, but the imidazole compound can easily maintain its shape at room temperature, and is excellent in handleability. In the case of a crystalline solid having a melting point of 250 ° C. or lower, not only the curability at a temperature of 25 ° C. or higher is more excellent, but also the curing rate at a temperature of 250 ° C. or lower tends to be faster.

  In the present embodiment, it is preferable that particles having a powder shape and having a particle size of the core imidazole compound of 0.1 μm or more and 100 μm or less are composed of 10% by mass or more in the imidazole compound. The term “powdered” as used herein refers to a powder having a maximum particle size of 2 mm or less, for example, passed through a sieve having an opening of 2 mm or less. In the case of particles having a particle size of 2 mm or less, for example, when a cured product is obtained by blending with an epoxy resin, the components of the cured product tend to be uniformly cured.

  In the present embodiment, the maximum particle size is preferably 1 mm or less, more preferably 500 μm or less, and even more preferably 100 μm or less.

  In the present embodiment, it is preferable that particles of an imidazole compound having a particle size of 0.1 μm or more and 100 μm or less are contained in the imidazole compound in an amount of 30% by mass or more, and particles of 0.1 μm or more and 100 μm or less are contained in an amount of 90% by mass or more. It is more preferable that 90% by mass or more of particles of 0.1 μm or more and 50 μm or less are contained. In the present embodiment, ultrafine particles of 0.1 μm or less may be included.

  The particle shape and the overall particle distribution can be measured using a commercially available dry particle size distribution measuring device. For example, the particle size distribution of the imidazole compound can be measured by a dry method using a laser diffraction particle size distribution measuring device (HELOS / BF-M) manufactured by Nippon Laser.

  In the present embodiment, it is preferable that the maximum particle size of the imidazole compound is 500 μm or less, and particles having a particle size of 0.1 μm or more and 100 μm or less are contained in the imidazole compound in an amount of 30% by mass or more. More preferably, particles having a particle size of 100 μm or less and a particle size of 0.1 μm or more and 100 μm or less are 90% by mass or more, the maximum particle size is 100 μm or less, and the particle size is 0.1 μm or more and 50 μm or less. More preferably, 90% by mass or more of the particles are contained.

  In the imidazole compound-containing microencapsulated composition of the present embodiment, the core preferably contains an imidazole compound and a low molecular amine compound. The core of the imidazole compound-containing microencapsulated composition of the present embodiment contains an imidazole compound and a low-molecular amine compound. By adjusting the content of the low-molecular amine compound, the imidazole compound-containing microencapsulation is performed. It is preferable from the viewpoint that the melting point of the composition can be adjusted to a desired temperature, and further that low temperature curability can be imparted to the imidazole compound-containing microencapsulated composition.

  The content of the low molecular amine compound is preferably 0.1 ppm or more and 50,000 ppm or less in the core, and more preferably 0.1 ppm or more and 10,000 ppm or less (mass fraction). When the content of the low-molecular amine compound is 50,000 ppm or less, a significant decrease in the melting point of the mixture with the imidazole compound can be suppressed, and when it is blended with an epoxy resin after microencapsulation, the storage stability is further improved. There is a tendency to improve.

  The low-molecular amine compound is specifically an organic compound having a molecular weight of 2000 or less and having at least one primary amino group, secondary amino group, or tertiary amino group in the molecule, Two or more different amino groups may be present in the same molecule at the same time.

  Examples of the compound having a primary amino group include methylamine, ethylamine, propylamine, butylamine, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, ethanolamine, propanolamine, cyclohexylamine, isophoronediamine, Examples include aniline, toluidine, diaminodiphenylmethane, diaminodiphenylsulfone and the like.

  Examples of the compound having a secondary amino group include dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, dimethanolamine, diethanolamine, dipropanolamine, dicyclohexylamine, piperidine, piperidone, diphenylamine, Examples include phenylmethylamine and phenylethylamine.

  Examples of the compound having a tertiary amino group include trimethylamine, triethylamine, benzyldimethylamine, N, N′-dimethylpiperazine, triethylenediamine, 1,8-diazabicyclo (5,4,0) -undecene-7, 1 , Tertiary amines such as 5-diazabicyclo (4,3,0) -nonene-5; 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, Amino alcohols such as 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, methyldiethanolamine, triethanolamine, N-β-hydroxyethylmorpholine; 2- (dimethylaminomethyl) phenol, 2,4,6 -Tris (dimethylaminome L) Aminophenols such as phenol; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1- (2-hydroxy-3-phenoxy) Propyl) -2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-ethyl-4-methylimidazole, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazole, 1- Imidazoles such as (2-hydroxy-3-butoxypropyl) -2-ethyl-4-methylimidazole; 1- (2-hydroxy-3-phenoxypropyl) -2-phenylimidazoline, 1- (2-hydroxy-3 -Butoxypropyl) -2-methylimidazoline, 2-methylimid Dazoline, 2,4-dimethylimidazoline, 2-ethylimidazoline, 2-ethyl-4-methylimidazoline, 2-benzylimidazoline, 2-phenylimidazoline, 2- (o-tolyl) -imidazoline, tetramethylene-bis-imidazoline, 1,1,3-trimethyl-1,4-tetramethylene-bis-imidazoline, 1,3,3-trimethyl-1,4-tetramethylene-bis-imidazoline, 1,1,3-trimethyl-1,4- Tetramethylene-bis-4-methylimidazoline, 1,3,3-trimethyl-1,4-tetramethylene-bis-4-methylimidazoline, 1,2-phenylene-bis-imidazoline, 1,3-phenylene-bis- Imidazoline, 1,4-phenylene-bis-imidazoline, 1,4-phenylene-bis-4-me Imidazolines such as loumidazoline, dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, dipropylaminoethylamine, dibutylaminoethylamine, N-methylpiperazine, N- Tertiary aminoamines such as aminoethylpiperazine and diethylaminoethylpiperazine; aminomercaptans such as 2-dimethylaminoethanethiol, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptopyridine and 4-mercaptopyridine; Aminocarboxylic acids such as N, N-dimethylaminobenzoic acid, N, N-dimethylglycine, nicotinic acid, isonicotinic acid and picolinic acid ; N, N-dimethylglycine hydrazide, hydrazide nicotinate, amino hydrazides such as isonicotinic acid hydrazide and the like.

  Examples of the compound having two or more different amino groups in the same molecule at the same time include, for example, an amino group-containing imidazole compound used as a raw material of the present embodiment, and 1-aminoethyl-2-methylimidazoline. Primary amino group-containing imidazoline compounds such as 1-aminopropyl-2-methylimidazoline, and the like.

  As the low molecular weight amino compound, imidazoles, imidazolines, and amino group-containing imidazoles are preferable from the viewpoint of storage stability of the composition when blended in an epoxy resin.

  Hereinafter, the manufacturing method of the imidazole compound which is the core of the imidazole compound containing microencapsulated composition of this Embodiment is demonstrated.

  The manufacturing method of the imidazole compound of this Embodiment has at least the process of synthesize | combining an imidazole compound, and the powdering process of grind | pulverizing to a desired particle size. You may further have the refinement | purification process of this compound, the classification process of particle | grains, and the re-blending process of the particle | grain of each particle size as needed. The low molecular amine compound may be present as an unreacted component in the step of synthesizing the imidazole compound, or may be separately added to the imidazole compound.

  The manufacturing method of the imidazole compound used by this Embodiment can be manufactured by the well-known method described in patent document 1 or patent document 2. That is, it can be produced by reacting an amino group-containing imidazole compound represented by the above formula (3) with a compound having an isocyanate group, a thioisocyanate group, a carboxyl group, or a carbodithio group.

  A method for producing an imidazole compound having a urea bond that is preferably used in the present embodiment will be described. The imidazole compound having a urea bond that is preferably used in the present embodiment is an amino group-containing imidazole compound represented by the above formula (3) and an isocyanate group-containing compound (hereinafter may be collectively referred to as an isocyanate compound). And can be synthesized. In addition, for example, an imidazole compound having a urea bond can be synthesized by reacting an imidazoline compound containing an amino group with an isocyanate compound and converting the imidazoline moiety into an imidazole structure by a dehydrogenation reaction in a subsequent step.

  The amino group-containing imidazole compound is represented by the above formula (3), and Q in the formula is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain a substituent. The hydrocarbon group is a saturated hydrocarbon group, an unsaturated hydrocarbon group having a double bond inside, or an aromatic group which may have an aromatic ring. The hydrocarbon group may have a straight chain structure or a branched structure, and may have an alicyclic structure. Examples of the substituent include halogen groups such as fluorine, chlorine and bromine, acyl groups, amino groups, nitrile groups and hydroxyl groups. The number of carbon atoms in Q is preferably 3-20, more preferably 3-10, still more preferably 3-6, and even more preferably 3-4. Q preferably has any structure represented by the following formula (2).

  Specific examples of the amino group-containing imidazole compound include, in the above formula (3), when Q is a methylene group, 1-aminomethyl-imidazole, 1-aminomethyl-2-methylimidazole, 1-aminomethyl- 2-ethylimidazole, 1-aminomethyl-2-propylimidazole, 1-aminomethyl-2-butylimidazole, 1-aminomethyl-2-hexylimidazole, 1-aminomethyl-2-pentylimidazole, 1-aminomethyl- 2-peptylimidazole, 1-aminomethyl-2-octylimidazole, 1-aminomethyl-2-nonylimidazole, 1-aminomethyl-2-decylimidazole, 1-aminomethyl-2-undecylimidazole, 1-amino Methyl-2-heptadecylimidazole, 1- Minomethyl-2-phenylimidazole, 1-aminomethyl-2-methyl-4,5-dihydroxymethylimidazole, 1-aminomethyl-2-ethyl-4,5-dihydroxymethylimidazole, 1-aminomethyl-2-phenyl- 4,5-dihydroxymethylimidazole, 1-aminomethyl-2-undecyl-4,5-dihydroxymethylimidazole, 1-aminomethyl-2-heptadecyl-4,5-dihydroxymethylimidazole, 1-aminomethyl-2-methyl -4-methyl-5-hydroxymethylimidazole, 1-aminomethyl-2-ethyl-4-methyl-5-hydroxymethylimidazole, 1-aminomethyl-2-phenyl-4-methyl-5-hydroxymethylimidazole, 1 -Aminomethyl-2-undecyl- -Methyl-5-hydroxymethylimidazole, 1-aminomethyl-2-heptadecyl-4-methyl-5-hydroxymethylimidazole, 1-aminomethyl-4-methylimidazole, 1-aminomethyl-2-methyl-4-methyl Imidazole, 1-aminomethyl-2-ethyl-4-methylimidazole, 1-aminomethyl-2-propyl-4-methylimidazole, 1-aminomethyl-2-butyl-4-methylimidazole, 1-aminomethyl-2 -Hexyl-4-methylimidazole, 1-aminomethyl-2-pentyl-4-methylimidazole, 1-aminomethyl-2-peptyl-4-methylimidazole, 1-aminomethyl-2-octyl-4-methylimidazole, 1-aminomethyl-2-nonyl-4-methylimidazole, 1 -Aminomethyl-2-decyl-4-methylimidazole, 1-aminomethyl-2-undecyl-4-methylimidazole, 1-aminomethyl-2-heptadecyl-4-methylimidazole, 1-aminomethyl-2-methoxyimidazole 1-aminomethyl-2-methoxy-4-methylimidazole, 1-aminomethyl-2-methoxy-4,5-dihydroxymethylimidazole, 1-aminomethyl-2-methoxy-4-methyl-5-hydroxymethylimidazole 1-aminomethyl-2-ethoxyimidazole, 1-aminomethyl-2-ethoxy-4-methylimidazole, 1-aminomethyl-2-ethoxy-4,5-dihydroxymethylimidazole, 1-aminomethyl-2-ethoxy -4-Methyl-5-hydroxymethylimidazole 1-aminomethyl-2-phenoxyimidazole, 1-aminomethyl-2-phenoxy-4-methylimidazole, 1-aminomethyl-2-phenoxy-4,5-dihydroxymethylimidazole, 1-aminomethyl-2-phenoxy Examples include -4-methyl-5-hydroxymethylimidazole.

  Examples of the case where Q is an ethylene group include 1-aminoethyl-imidazole, 1-aminoethyl-2-methylimidazole, 1-aminoethyl-2-ethylimidazole, 1-aminoethyl-2-propylimidazole. 1-aminoethyl-2-butylimidazole, 1-aminoethyl-2-hexylimidazole, 1-aminoethyl-2-pentylimidazole, 1-aminoethyl-2-peptylimidazole, 1-aminoethyl-2-octyl Imidazole, 1-aminoethyl-2-nonylimidazole, 1-aminoethyl-2-decylimidazole, 1-aminoethyl-2-undecylimidazole, 1-aminoethyl-2-heptadecylimidazole, 1-aminoethyl-2 -Phenylimidazole, 1-aminoethyl- -Methyl-4,5-dihydroxymethylimidazole, 1-aminoethyl-2-ethyl-4,5-dihydroxymethylimidazole, 1-aminoethyl-2-phenyl-4,5-dihydroxymethylimidazole, 1-aminoethyl- 2-undecyl-4,5-dihydroxymethylimidazole, 1-aminoethyl-2-heptadecyl-4,5-dihydroxymethylimidazole, 1-aminoethyl-2-methyl-4-methyl-5-hydroxymethylimidazole, 1- Aminoethyl-2-ethyl-4-methyl-5-hydroxymethylimidazole, 1-aminoethyl-2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-aminoethyl-2-undecyl-4-methyl-5 -Hydroxymethylimidazole, 1-aminoe Ru-2-heptadecyl-4-methyl-5-hydroxymethylimidazole, 1-aminoethyl-4-methylimidazole, 1-aminoethyl-2-methyl-4-methylimidazole, 1-aminoethyl-2-ethyl-4 -Methylimidazole, 1-aminoethyl-2-propyl-4-methylimidazole, 1-aminoethyl-2-butyl-4-methylimidazole, 1-aminoethyl-2-hexyl-4-methylimidazole, 1-aminoethyl 2-pentyl-4-methylimidazole, 1-aminoethyl-2-peptyl-4-methylimidazole, 1-aminoethyl-2-octyl-4-methylimidazole, 1-aminoethyl-2-nonyl-4-methyl Imidazole, 1-aminoethyl-2-decyl-4-methylimidazole, 1-a Minoethyl-2-undecyl-4-methylimidazole, 1-aminoethyl-2-heptadecyl-4-methylimidazole, 1-aminoethyl-2-methoxyimidazole, 1-aminoethyl-2-methoxy-4-methylimidazole, 1 -Aminoethyl-2-methoxy-4,5-dihydroxymethylimidazole, 1-aminoethyl-2-methoxy-4-methyl-5-hydroxymethylimidazole, 1-aminoethyl-2-ethoxyimidazole, 1-aminoethyl- 2-ethoxy-4-methylimidazole, 1-aminoethyl-2-ethoxy-4,5-dihydroxymethylimidazole, 1-aminoethyl-2-ethoxy-4-methyl-5-hydroxymethylimidazole, 1-aminoethyl- 2-phenoxyimidazole, 1-amino Examples include ethyl-2-phenoxy-4-methylimidazole, 1-aminoethyl-2-phenoxy-4,5-dihydroxymethylimidazole, 1-aminoethyl-2-phenoxy-4-methyl-5-hydroxymethylimidazole, and the like. .

  Examples of the case where Q is a linear or branched propylene group having 3 carbon atoms include, for example, 1-aminopropyl-imidazole, 1-aminopropyl-2-methylimidazole, 1-aminopropyl-2-ethylimidazole 1-aminopropyl-2-propylimidazole, 1-aminopropyl-2-butylimidazole, 1-aminopropyl-2-hexylimidazole, 1-aminopropyl-2-pentylimidazole, 1-aminopropyl-2-peptyl Imidazole, 1-aminopropyl-2-octylimidazole, 1-aminopropyl-2-nonylimidazole, 1-aminopropyl-2-decylimidazole, 1-aminopropyl-2-undecylimidazole, 1-aminopropyl-2- Heptadecylimidazole, 1-amino Propyl-2-phenylimidazole, 1-aminopropyl-2-methyl-4,5-dihydroxymethylimidazole, 1-aminopropyl-2-ethyl-4,5-dihydroxymethylimidazole, 1-aminopropyl-2-phenyl- 4,5-dihydroxymethylimidazole, 1-aminopropyl-2-undecyl-4,5-dihydroxymethylimidazole, 1-aminopropyl-2-heptadecyl-4,5-dihydroxymethylimidazole, 1-aminopropyl-2-methyl -4-methyl-5-hydroxymethylimidazole, 1-aminopropyl-2-ethyl-4-methyl-5-hydroxymethylimidazole, 1-aminopropyl-2-phenyl-4-methyl-5-hydroxymethylimidazole, 1 -Aminopropyl- -Undecyl-4-methyl-5-hydroxymethylimidazole, 1-aminopropyl-2-heptadecyl-4-methyl-5-hydroxymethylimidazole, 1-aminopropyl-4-methylimidazole, 1-aminopropyl-2-methyl -4-methylimidazole, 1-aminopropyl-2-ethyl-4-methylimidazole, 1-aminopropyl-2-propyl-4-methylimidazole, 1-aminopropyl-2-butyl-4-methylimidazole, 1- Aminopropyl-2-hexyl-4-methylimidazole, 1-aminopropyl-2-pentyl-4-methylimidazole, 1-aminopropyl-2-peptyl-4-methylimidazole, 1-aminopropyl-2-octyl-4 -Methylimidazole, 1-aminopropyl- 2-nonyl-4-methylimidazole, 1-aminopropyl-2-decyl-4-methylimidazole, 1-aminopropyl-2-undecyl-4-methylimidazole, 1-aminopropyl-2-heptadecyl-4-methylimidazole 1-aminopropyl-2-methoxyimidazole, 1-aminopropyl-2-methoxy-4-methylimidazole, 1-aminopropyl-2-methoxy-4,5-dihydroxymethylimidazole, 1-aminopropyl-2-methoxy -4-methyl-5-hydroxymethylimidazole, 1-aminopropyl-2-ethoxyimidazole, 1-aminopropyl-2-ethoxy-4-methylimidazole, 1-aminopropyl-2-ethoxy-4,5-dihydroxymethyl Imidazole, 1-aminopropi 2-ethoxy-4-methyl-5-hydroxymethylimidazole, 1-aminopropyl-2-phenoxyimidazole, 1-aminopropyl-2-phenoxy-4-methylimidazole, 1-aminopropyl-2-phenoxy-4, Examples include 5-dihydroxymethylimidazole and 1-aminopropyl-2-phenoxy-4-methyl-5-hydroxymethylimidazole.

  Examples of the case where Q is a linear or branched butylene group having 4 carbon atoms include 1-aminobutyl-imidazole, 1-aminobutyl-2-methylimidazole, 1-aminobutyl-2-ethylimidazole. 1-aminobutyl-2-propylimidazole, 1-aminobutyl-2-butylimidazole, 1-aminobutyl-2-hexylimidazole, 1-aminobutyl-2-pentylimidazole, 1-aminobutyl-2-peptyl Imidazole, 1-aminobutyl-2-octylimidazole, 1-aminobutyl-2-nonylimidazole, 1-aminobutyl-2-decylimidazole, 1-aminobutyl-2-undecylimidazole, 1-aminobutyl-2- Heptadecylimidazole, 1-aminobutyl-2-phenylimida 1-aminobutyl-2-methyl-4,5-dihydroxymethylimidazole, 1-aminobutyl-2-ethyl-4,5-dihydroxymethylimidazole, 1-aminobutyl-2-phenyl-4,5- Dihydroxymethylimidazole, 1-aminobutyl-2-undecyl-4,5-dihydroxymethylimidazole, 1-aminobutyl-2-heptadecyl-4,5-dihydroxymethylimidazole, 1-aminobutyl-2-methyl-4-methyl -5-hydroxymethylimidazole, 1-aminobutyl-2-ethyl-4-methyl-5-hydroxymethylimidazole, 1-aminobutyl-2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-aminobutyl- 2-Undecyl-4-methyl-5-hydroxymethyl Midazole, 1-aminobutyl-2-heptadecyl-4-methyl-5-hydroxymethylimidazole, 1-aminobutyl-4-methylimidazole, 1-aminobutyl-2-methyl-4-methylimidazole, 1-aminobutyl- 2-ethyl-4-methylimidazole, 1-aminobutyl-2-propyl-4-methylimidazole, 1-aminobutyl-2-butyl-4-methylimidazole, 1-aminobutyl-2-hexyl-4-methylimidazole 1-aminobutyl-2-pentyl-4-methylimidazole, 1-aminobutyl-2-peptyl-4-methylimidazole, 1-aminobutyl-2-octyl-4-methylimidazole, 1-aminobutyl-2- Nonyl-4-methylimidazole, 1-aminobutyl-2-decyl-4- Methylimidazole, 1-aminobutyl-2-undecyl-4-methylimidazole, 1-aminobutyl-2-heptadecyl-4-methylimidazole, 1-aminobutyl-2-methoxyimidazole, 1-aminobutyl-2-methoxy- 4-methylimidazole, 1-aminobutyl-2-methoxy-4,5-dihydroxymethylimidazole, 1-aminobutyl-2-methoxy-4-methyl-5-hydroxymethylimidazole, 1-aminobutyl-2-ethoxyimidazole 1-aminobutyl-2-ethoxy-4-methylimidazole, 1-aminobutyl-2-ethoxy-4,5-dihydroxymethylimidazole, 1-aminobutyl-2-ethoxy-4-methyl-5-hydroxymethylimidazole 1-aminobutyl-2-pheno Siimidazole, 1-aminobutyl-2-phenoxy-4-methylimidazole, 1-aminobutyl-2-phenoxy-4,5-dihydroxymethylimidazole, 1-aminobutyl-2-phenoxy-4-methyl-5-hydroxy And methyl imidazole.

  Among these, those having a structure of the imidazole moiety of the 2-methylimidazole type are preferable because the curing rate tends to increase, and further, Q in the above formula (3) to which an amino group is bonded has 2 to 4 carbon atoms. What is a bivalent hydrocarbon residue is more preferable, and what is a C3-C4 divalent hydrocarbon residue is still more preferable. A specific example of a preferred amino group-containing imidazole compound is shown in the following formula (5).

  Among these, from the viewpoint of further excellent low-temperature curability, any amino group-containing imidazole compound represented by the following formula (5a) is particularly preferable.

  Examples of the isocyanate compound include monoisocyanates, diisocyanates, triisocyanates, and polyisocyanates. For example, monoisocyanates include ethyl isocyanate, propyl isocyanate, isopropyl isocyanate, n-butyl isocyanate, n-hexyl isocyanate, cyclohexyl isocyanate, pentyl isocyanate, heptyl isocyanate, octyl isocyanate, 2-ethylhexyl isocyanate, nonyl isocyanate, decyl isocyanate, Aliphatic monoisocyanates such as dodecyl isocyanate, tridecyl isocyanate, tetradecyl isocyanate, hexadecyl isocyanate, octadecyl isocyanate, isocyanate ethyl methacrylate, isocyanate ethyl acrylate, phenyl isocyanate, benzyl isocyanate, phenethyl isocyanate, toluidine iso Aneto, p- chlorophenyl isocyanate, 3,4-dichlorophenyl isocyanate, an aromatic monoisocyanate such as naphthyl isocyanate.

  Examples of the diisocyanate include ethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, xylylene diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate. 4,4′-diphenylmethane diisocyanate, dianisidine diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, chlorophenylene-2,4-diisocyanate, 1,5-naphthalene diisocyanate, diethylidene diisocyanate, propylene-1,2-diisocyanate, Cyclohexylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene Isocyanate, 3,3′-dimethoxy-4,4′-biphenylene diisocyanate, 3,3′-diphenyl-4,4′-diphenyl-biphenylene diisocyanate, 3,3′-dichloro-4,4′-biphenylene diisocyanate, norbornane Examples include diisocyanate and 1,3-bis (isocyanatomethyl) cyclohexane.

  Examples of triisocyanates include hexamethylene diisocyanate bilet, hexamethylene diisocyanate isocyanurate, hexamethylene diisocyanate and aliphatic triol adduct, isophorone diisocyanate bilet, isophorone diisocyanate isocyanurate, isophorone diisocyanate and fat. Examples include adducts with group triols, triphenylmethane triisocyanate, and the like.

  Moreover, as polyisocyanate, polymeric diphenylmethane diisocyanate etc. are mentioned, for example.

  The imidazole compound having a urea bond that is preferably used in the present embodiment can be obtained by reacting the amino group-containing imidazole compound and an isocyanate compound in the absence of a solvent or in the presence of a solvent. The solvent is not particularly limited as long as it does not react with the amino group-containing imidazole compound, the isocyanate compound, and the imidazole compound having a urea bond to be formed, or does not form a salt. Examples of such solvents include dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether, ethers such as ethylene glycol dimethyl ether, diethylene glycol, and tetrahydrofuran, esters such as methyl acetate and ethyl acetate, benzene, hexane, and cyclohexane. , Hydrocarbons such as toluene, xylene and benzene, and nitriles such as acetonitrile, propionitrile and benzonitrile. These solvents may be good solvents that dissolve the resulting imidazole compound, or may be poor solvents that do not dissolve.

  Although reaction temperature is not specifically limited, Usually, it implements in the range of -20 degreeC-150 degreeC. Preferably it is -10 degreeC-100 degreeC, More preferably, it is 10 degreeC-80 degreeC. When the reaction temperature is 150 ° C. or lower, the yield of the obtained imidazole compound tends to be high.

  The imidazole compound synthesized by the above reaction can be obtained by removing the solvent by evaporation or the like when a solvent is used in the reaction. When a poor solvent that does not dissolve the desired imidazole compound is used, the desired imidazole compound can be easily obtained by performing filtration at the end of the reaction.

  It is also possible to set conditions so that an imidazole compound having a desired particle size is precipitated by appropriately selecting a solvent for the reaction. In addition, for the purpose of further increasing the purity of the imidazole compound, the obtained imidazole compound is washed with a poor solvent, or purification such as crystallization is performed using the same solvent as the solvent used in the synthesis or another solvent. Also good.

  In the production of the imidazole compound used in the present embodiment, the pulverization step is preferably performed through the synthesis step or the subsequent purification step. In the pulverization step, the powdery imidazole compound obtained above may be used as it is, or the solid obtained by melting the imidazole compound obtained above at a melting point or higher and cooling it is used. Also good.

  The pulverization method performed in the pulverization step is not particularly limited, for example, a method of pulverizing with a mortar, a method of pulverizing using a ball mill, a difference in solubility due to temperature after dissolving in a solvent, or using a poor solvent Reprecipitation by phase separation, method of obtaining fine powder by spray drying method after dissolving in solvent, method of obtaining fine powder by wet ultrahigh pressure method by dispersing in poor solvent, high pressure jet stream such as air Examples include a method of pulverizing with a jet mill used.

  In the present embodiment, an imidazole compound having a desired particle diameter may be obtained by only one kind of the above-described various methods, or two or more kinds of various grinding methods may be combined. Furthermore, the fine powder obtained by the various methods described above may be classified into each particle size and adjusted by re-blending so that the desired particle size has a desired content.

  Among the above pulverization methods, a method of obtaining a fine powder by spray drying after being dissolved in a solvent, a method of obtaining a fine powder by dispersing in a poor solvent and a wet ultrahigh pressure method, a jet mill using a high-pressure jet stream such as air Is preferable. These methods are preferable because an imidazole compound having a particle size of 100 μm or less can be obtained in a high yield. Among them, a method of pulverizing with a jet mill using a high-pressure jet stream such as air is more preferable. According to this method, an imidazole compound having a particle size of 50 μm or less can be obtained in high yield. In the method of pulverizing with a jet mill, a commercially available dry jet mill apparatus can be used. For example, Nanojet Mizer manufactured by Aisin Nano Technologies, Inc. can be preferably used.

  The low molecular amine compound in the present embodiment may be left in the composition as an unreacted component during the production of the imidazole compound, or may be added separately to the imidazole compound.

  The shape of the imidazole compound in the present embodiment is not particularly limited, and may be spherical or indefinite. For example, when it is spherical, when blended with an epoxy resin, the composition tends to decrease in viscosity. Here, the term “spherical” includes not only true spheres but also shapes with rounded indefinite corners. In the case of an indeterminate shape, the contact surface tends to increase when blended with an epoxy resin.

  The imidazole compound in the present embodiment is preferably in the form of granules or powder, more preferably in the form of powder. Here, the powder form is not particularly limited, but the average particle size is preferably 0.1 to 50 μm, more preferably 0.5 to 10 μm. The particle diameter refers to the Stokes diameter measured by the light scattering method. The average particle diameter refers to the median diameter.

  The imidazole compound-containing microencapsulated composition of the present embodiment has a structure in which the surface of a core containing an imidazole compound is covered with a shell containing an organic polymer, an inorganic compound, or both.

  Although content of the shell with respect to a core is not specifically limited, It is preferable that it is 0.01-100 mass parts with respect to 100 mass parts of cores, and it is more preferable that it is 0.1-80 mass parts. It is more preferable that it is -60 mass parts, and it is still more preferable that it is 5-50 mass parts.

  Examples of the organic polymer include natural polymers such as cellulose, natural rubber, starch and protein, and synthetic resins. Among these, a synthetic resin is preferable from the viewpoints of storage stability, ease of breaking of the shell during curing, and uniformity of physical properties of the cured product.

  Examples of synthetic resins include epoxy resins, acrylic resins, polyester resins, phenol resins, polyethylene resins, nylon resins, polystyrene resins, urea resins, urethane resins, and mixtures and copolymers thereof. Among these, phenol resins, urethane resins that are addition products of mono- or polyhydric alcohols and mono- or polyisocyanates, polymers having two or more types of urea bonds, urethane bonds, and burette bonds at the same time, amine compounds, Reaction products with epoxy resins, and mixtures and copolymers thereof are preferred. The amine compound may be a compound having a normal primary amino group or secondary amino group, or may be a compound obtained by decomposing an isocyanate compound with water and modifying it to an amino group.

  Examples of the inorganic compound include boron compounds such as boron oxide and boric acid ester, silicon dioxide, calcium oxide, and the like. Among these, boron oxide is preferable from the viewpoints of shell stability and ease of destruction during heating.

In the present embodiment, a urethane resin in which the shell is an addition product of mono- or polyhydric alcohol and mono- or polyisocyanate, a polymer having two or more types of urea bond, urethane bond, and burette bond, amine compound a reaction product of an epoxy resin, and the case of a mixture or copolymers of these, absorbent bonded group that absorbs infrared wave number 1630～1680Cm ^-1 (x) and the infrared wave number 1680～1725Cm ^-1 It is preferable from the viewpoint of the balance between storage stability and reactivity that at least the bonding group (y) is present on the surface.

  The infrared absorption of the bonding group (x) and the bonding group (y) can be measured using a Fourier transform infrared spectrophotometer (hereinafter referred to as “FT-IR”). Moreover, it can be measured using microscopic FT-IR that the linking group (x) and / or the linking group (y) has at least the surface (that is, the shell) of the imidazole compound-containing microencapsulated composition. Of the bonding groups (x), a urea bond is particularly useful. Among the linking groups (y), a buret bond is particularly useful. What has this urea bond and burette bond is a reaction product produced | generated by reaction of an isocyanate compound and an active hydrogen compound.

  As an isocyanate compound used to generate a urea bond that is representative of the above-mentioned bonding group (x) and a burette bond that is representative of the bonding group (y), it has one or more isocyanate groups in one molecule. Although it may be a compound, it is preferably a compound having two or more isocyanate groups in one molecule. Preferred isocyanates include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, low molecular triisocyanates, and polyisocyanates.

  Specific examples of the aliphatic diisocyanate include ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate.

  Specific examples of the alicyclic diisocyanate include isophorone diisocyanate, 4-4′-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,4-isocyanatocyclohexane, 1,3-bis (isocyanatomethyl) -cyclohexane, 1,3- Bis (2-isocyanatopropyl-2-yl) -cyclohexane and the like can be mentioned.

  Specific examples of the aromatic diisocyanate include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylene diisocyanate, 1,5-naphthalene diisocyanate, and the like. Examples of low molecular weight triisocyanates include 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, 2,6-diisocyanatohexane Aliphatic triisocyanate compounds such as acid-2-isocyanatoethyl and 2,6-diisocyanatohexanoic acid-1-methyl-2-isocyanatoethyl, alicyclic triisocyanates such as tricyclohexylmethane triisocyanate and bicycloheptane triisocyanate Examples thereof include aromatic triisocyanate compounds such as isocyanate compounds, triphenylmethane triisocyanate, and tris (isocyanatephenyl) thiophosphate.

  Examples of the polyisocyanate include polymethylene polyphenyl polyisocyanate, polyisocyanate derived from the above diisocyanate, and low molecular triisocyanate. Examples of the polyisocyanate derived from the diisocyanate and triisocyanate include isocyanurate type polyisocyanate, burette type polyisocyanate, urethane type polyisocyanate, allophanate type polyisocyanate, carbodiimide type polyisocyanate and the like. These isocyanate compounds can be used in combination.

  Examples of the active hydrogen compound for generating a urea bond that is representative of the linking group (x) and a burette bond that is representative of the linking group (y) include water, one or more primary and / or Alternatively, a compound having a secondary amino group and a compound having one or more hydroxyl groups in one molecule may be mentioned. These may be used in combination. Among these, water and a compound having one or more hydroxyl groups in one molecule are preferable.

  As the compound having one or more primary and / or secondary amino groups in one molecule, aliphatic amine, alicyclic amine, and aromatic amine can be used.

  Specific examples of the aliphatic amine include alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine; alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, and hexamethylenediamine; diethylenetriamine, triethylenetetramine, tetraethylene Examples include polyalkylene polyamines such as pentamine; polyoxyalkylene polyamines such as polyoxypropylene diamine and polyoxyethylene diamine.

  Specific examples of the alicyclic amine include cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, isophoronediamine and the like. Specific examples of the aromatic amine include aniline, toluidine, benzylamine, naphthylamine, diaminodiphenylmethane, diaminodiphenylsulfone and the like.

  Examples of the compound having one or more hydroxyl groups in one molecule used as the active hydrogen compound include alcohol compounds and phenol compounds. Examples of alcohol compounds include methyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, dodecyl alcohol, stearyl alcohol, eicosyl alcohol, Monoalcohols such as allyl alcohol, crotyl alcohol, propargyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, cinnamyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol monobutyl, Ethylene glycol, polyethylene glycol, propylene Recall, polypropylene glycol, 1,3-butanediol, 1,4-butanediol, hydrogenated bisphenol A, neopentyl glycol, glycerol, trimethylolpropane, polyhydric alcohols such as pentaerythritol.

  Also, by reaction of a compound having one or more epoxy groups in one molecule with a compound having one or more hydroxyl groups, carboxyl groups, primary or secondary amino groups, or mercapto groups in one molecule. The resulting compound having two or more secondary hydroxyl groups in one molecule is also exemplified as polyhydric alcohols. These alcohol compounds may be primary, secondary, or tertiary alcohols. Examples of the phenol compound include monophenols such as carboxylic acid, cresol, xylenol, carvacrol, motile, and naphthol, and polyhydric phenols such as catechol, resorcin, hydroquinone, bisphenol A, bisphenol F, pyrogallol, and phloroglucin. As the compound having one or more hydroxyl groups in one molecule, polyhydric alcohols and polyhydric phenols are preferable. Polyhydric alcohols are more preferred.

  In the shell, the linking group (x) is preferably at a concentration in the range of 1 to 1000 meq / kg. Moreover, it is preferable that a coupling | bonding group (y) is the density | concentration of the range of 1-1-1000 meq / kg.

  The concentration here is the concentration of the linking group relative to the unit mass of the core. By setting the concentration of the bonding group (x) to 1 meq / kg or more, a capsule-type curing agent having high resistance to mechanical shearing force can be obtained. Moreover, high sclerosis | hardenability can be acquired by setting it as 1000 meq / kg or less. A more preferable concentration range of the linking group (x) is 10 to 300 meq / kg.

  By setting the concentration of the bonding group (y) to 1 meq / kg or more, a capsule-type curing agent having high resistance to mechanical shearing force can be obtained. Moreover, high sclerosis | hardenability can be acquired by setting it as 1000 meq / kg or less. A more preferable range of the linking group (y) is 10 to 200 meq / kg.

The shell preferably further has a bonding group (z) that absorbs infrared rays having a wave number of 1730 to 1755 cm ⁻¹ . The infrared absorption of the bonding group (z) can also be measured using a Fourier transform infrared spectrophotometer (FT-IR). Moreover, it can be measured using microscopic FT-IR that the linking group (z) has at least the surface of the core mainly composed of an imidazole compound.

  Of these linking groups (z), a particularly useful one is a urethane bond. This urethane bond is generated by a reaction between an isocyanate compound and a compound having one or more hydroxyl groups in one molecule. As the isocyanate compound used here, an isocyanate compound used for generating a urea bond or a burette bond can be used.

  Examples of the compound having one or more hydroxyl groups in one molecule used to form a urethane bond that is representative of the bonding group (z) include aliphatic saturated alcohols, aliphatic unsaturated alcohols, aliphatic alcohols, and aromatics. Alcohol compounds such as alcohol and phenol compounds can be used.

  Aliphatic alcohols include methyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, dodecyl alcohol, stearyl alcohol, eicosyl alcohol Monoalcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoalkyl ethers such as ethylene glycol monohexyl ether; ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1, Tetravalent such as 3-butanediol and neopentyl glycol Alcohols such; glycerin, trimethylol, trihydric alcohols such as propane; tetravalent alcohols such as pentaerythritol and the like. Examples of the aliphatic unsaturated alcohol include allyl alcohol, crotyl alcohol, propargyl alcohol and the like. Examples of the alicyclic alcohol include cyclopentanol, cyclohexanol, and cyclohexanedimethanol. Examples of the aromatic alcohol include monoalcohols such as benzyl alcohol and cinnamyl alcohol. These alcohols may be primary, secondary, or tertiary alcohols.

  Also obtained by reaction of a compound having one or more epoxy groups in one molecule with a compound having one or more hydroxyl groups, carboxyl groups, primary or secondary amino groups, or mercapto groups in one molecule. A compound having at least one secondary hydroxyl group in one molecule can also be used as the alcohol compound.

  Examples of the phenol compound include monohydric phenols such as carboxylic acid, cresol, xylenol, carvacrol, motile, naphthol, dihydric phenols such as catechol, resorcin, hydroquinone, bisphenol A, bisphenol F, and trivalent phenols such as pyrogallol and phloroglucin. It is done. A compound having one or more hydroxyl groups in one molecule is preferably an alcohol compound or a phenol compound having a divalent or higher hydroxyl group.

  A preferable concentration range of the bonding group (z) of the shell is 1 to 200 meq / kg. The concentration here is the concentration of the linking group relative to the unit mass of the shell. By setting the concentration of the bonding group (z) to 1 meq / kg or more, a shell having high resistance to mechanical shearing force can be formed. Moreover, high curability can be obtained by setting it as 200 meq / kg or less. A more preferable concentration range of the linking group (z) is 5 to 100 meq / kg. The concentration of the linking group (x), the linking group (y), and the linking group (z) can be quantified by the method disclosed in Japanese Patent Application Laid-Open No. 01-70523.

  The total thickness of the existence region of the bonding group (x), the bonding group (y) and the bonding group (z) of the shell is preferably 5 to 1000 nm in terms of an average layer thickness. Storage stability is obtained at 5 nm or more, and practical curability is obtained at 1000 nm or less. The thickness of a layer here can be measured with a transmission electron microscope. A particularly preferable total thickness of the bonding groups on the core surface is 10 to 100 nm in terms of an average layer thickness.

  The ratio of the bonding group to the shell is preferably 100/1 to 100/100 by mass ratio. Within this range, both storage stability and curability are compatible. More preferably, it is 100/2-100/80, More preferably, it is 100/5-100/60, More preferably, it is 100/10-100/50.

  As a method for causing a bonding group to exist in the shell, (1) the bonding group is precipitated in the shell by lowering the solubility of the bonding group component in a dispersion medium in which the shell is dispersed by dissolving the bonding group component. Method, (2) a method of forming a bonding group in a dispersion medium in which the shell is dispersed, and precipitating the bonding group in a shell mainly composed of an imidazole compound, and (3) bonding the shell as a reaction field. And a method of generating a group. Among these, the methods (2) and (3) are preferable because the reaction and the coating can be performed simultaneously.

  Here, examples of the dispersion medium include a solvent, a plasticizer, and resins. Moreover, an epoxy resin can also be used as a dispersion medium.

  Examples of the solvent include hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirit, and naphtha; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethyl acetate, n-butyl acetate, propylene glycol monomethyl ethyl ether Examples include esters such as acetate; alcohols such as methanol, isopropanol, n-butanol, butyl cellosolve, and butyl carbitol; water and the like. Plasticizers include dibutyl phthalate, di (2-ethylhexyl) phthalate diesters, aliphatic dibasic acid esters such as di (2-ethylhexyl) adipate, and tricresyl phosphate triphosphates. Examples thereof include glycol esters such as ester and polyethylene glycol esters. Examples of the resins include silicone resins, epoxy resins, and phenol resins.

  Examples of the epoxy resin that can be used as a dispersion medium in the method of coating the shell with a bonding group include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, and tetramethyl. Bisphenol type epoxy resin obtained by glycidylation of bisphenols such as bisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A; biphenol, dihydroxynaphthalene, dihydroxybenzene, 9,9-bis (4-hydroxyphenyl) fluorene Epoxy resins obtained by glycidylation of other dihydric phenols such as 1,1,1-tris (4-hydroxyphenyl) methane, -(1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) epoxy resin obtained by glycidylation of trisphenols such as bisphenol; 1,1,2,2, -tetrakis ( Epoxy resin obtained by glycidylation of tetrakisphenols such as 4-hydroxyphenyl) ethane; Novolac type epoxy resin obtained by glycidylation of novolaks such as phenol novolak, cresol novolak, bisphenol A novolak, brominated phenol novolak, brominated bisphenol A novolak Etc .; epoxy resins obtained by glycidylation of polyhydric phenols; aliphatic ether type epoxy resins obtained by glycidylation of polyhydric alcohols such as glycerin and polyethylene glycol; hydro such as p-oxybenzoic acid and β-oxynaphthoic acid Ether ester type epoxy resin in which xycarboxylic acid is glycidylated; Ester type epoxy resin in which polycarboxylic acid such as phthalic acid or terephthalic acid is glycidylated; Glycidylated product of amine compounds such as 4,4-diaminodiphenylmethane and m-aminophenol And glycidyl type epoxy resins such as amine type epoxy resins such as triglycidyl isocyanurate, and alicyclic epoxides such as 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate.

  Among them, a glycidyl type epoxy resin is preferable from the viewpoint of high storage stability of the epoxy resin composition, and an epoxy resin obtained by glycidylating polyhydric phenols is more preferable from the viewpoint of further improving the adhesiveness and heat resistance of the cured product. More preferred are epoxy resins obtained by glycidylation of bisphenol A, epoxy resins obtained by glycidylation of bisphenol F, and epoxy resins obtained by glycidylation of dihydroxynaphthalene.

  (3) In the method in which the shell is used as a reaction field to form a bonding group there, the reaction between the isocyanate compound and the active hydrogen compound is usually performed at a temperature range of -10 ° C to 150 ° C and a reaction time of 10 minutes to 12 hours. Can be done.

  The equivalent ratio of the isocyanate compound and the active hydrogen compound is not particularly limited. Usually, the equivalent ratio of the isocyanate group in the isocyanate compound to the active hydrogen in the active hydrogen compound is in the range of 1: 0.1 to 1: 1000. Used.

  When the reaction product obtained from the reaction between the core and the epoxy resin is used as the shell, the reaction is usually in the temperature range of 0 ° C. to 150 ° C., preferably 10 ° C. to 100 ° C., preferably 1 to 168 hours, preferably The reaction time is 2 hours to 72 hours, and can also be performed in a dispersion medium. Examples of the dispersion medium include a solvent and a plasticizer. Moreover, epoxy resin itself can also be used as a dispersion medium. In this case, the epoxy resin in the master batch type curing agent and the epoxy resin used for the shell forming reaction may be the same epoxy resin.

  Examples of the solvent include hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirit, and naphtha; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethyl acetate, n-butyl acetate, propylene glycol monomethyl ethyl ether Examples include esters such as acetate; alcohols such as methanol, isopropanol, n-butanol, butyl cellosolve, and butyl carbitol; water and the like.

  Examples of the plasticizer include phthalic acid diester plasticizers such as dibutyl phthalate and di (2-ethylhexyl) phthalate, aliphatic dibasic acid ester plasticizers such as di (2-ethylhexyl) adipate, and phosphoric acid. Examples include phosphate triester plasticizers such as tricresyl, and glycol ester plasticizers such as polyethylene glycol ester.

  The mass ratio when reacting the core and the epoxy resin used for the shell forming reaction is not particularly limited. Usually, the mass of the core with respect to the epoxy resin (the mass of the core / the mass of the epoxy resin) is 1000/1 to 1/10. , 000, preferably 100/1 to 1/100.

  When a reaction product obtained by the reaction between the core and the epoxy resin is used as the shell, as a method of covering the core with the shell, (a) the shell component is dissolved in the dispersion medium in which the core is dispersed. (B) a method in which the shell is deposited on the surface of the core by lowering the solubility of the components, (b) a method in which the shell is formed in the dispersion medium in which the core is dispersed, and the shell is deposited on the surface of the core. Examples include a method in which the surface of the core is used as a reaction field to form a shell there. Among these, the methods (b) and (c) are preferable because the reaction and the coating can be performed simultaneously. In the case of the latter (b) and (c), the epoxy resin curing agent of the present embodiment may use a low molecular weight amine compound in the core as a component for forming a shell, or may be added separately. Also good.

  The average thickness of the shell covering the surface of the core of the present embodiment is preferably 5 to 1000 nm. Storage stability is obtained at 5 nm or more, and practical curability is obtained at 1000 nm or less. The thickness of the layer here is observed with a transmission electron microscope. A particularly preferable shell thickness is 50 to 700 nm as an average layer thickness.

The epoxy resin used for the shell formation reaction is not particularly limited as long as the intended effect of the present embodiment is not impaired. Examples of such epoxy resins include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, Bisphenol type epoxy resin obtained by glycidylation of bisphenols such as tetrafluorobisphenol A; Epoxy resin obtained by glycidylation of other dihydric phenols such as biphenol and 9,9-bis (4-hydroxyphenyl) fluorene; 1-tris (4-hydroxyphenyl) methane, 4,4- (1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphene Epoxy resin obtained by glycidylation of trisphenols such as alcohol; epoxy resin obtained by glycidylation of tetrakisphenol such as 1,1,2,2, -tetrakis (4-hydroxyphenyl) ethane; phenol novolac, cresol novolac, bisphenol A novolak, novolak epoxy resin obtained by glycidylation of novolak such as A novolak, brominated phenol novolak, brominated bisphenol A novolak, etc .; epoxy resin obtained by glycidylation of polyhydric phenol, glycidylation of polyhydric alcohol such as glycerin and polyethylene glycol Aliphatic ether type epoxy resin; ether ester type epoxy resin obtained by glycidylation of hydroxycarboxylic acid such as p-oxybenzoic acid and β-oxynaphthoic acid; poly, such as phthalic acid and terephthalic acid Ester type epoxy resins obtained by glycidylation of carboxylic acid; glycidyl type epoxy resins such as glycidylated products of amine compounds such as 4,4-diaminodiphenylmethane and m-aminophenol, and amine type epoxy resins such as triglycidyl isocyanurate; And alicyclic epoxides such as 4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate.
These epoxy resins may be used alone or in combination of two or more.

  The total chlorine content of the epoxy resin used for the shell forming reaction is preferably 2500 ppm or less. More preferably, it is 2000 ppm or less, More preferably, it is 1500 ppm or less, More preferably, it is 800 ppm or less, More preferably, it is 400 ppm or less, More preferably, it is 180 ppm or less, More preferably, it is 100 ppm Or less, still more preferably 80 ppm or less, still more preferably 50 ppm or less. When the total chlorine content is 2500 ppm or less, an epoxy resin composition having a high balance between curability and storage stability can be obtained. The total chlorine amount can be measured by a method based on JIS K-7243-3.

  From the viewpoint of facilitating the control of the shell formation reaction, the total chlorine content of the epoxy resin used in the shell formation reaction is preferably 0.01 ppm or more. More preferably 0.02 ppm or more, still more preferably 0.05 ppm or more, still more preferably 0.1 ppm or more, still more preferably 0.2 ppm or more, and still more preferably 0.5 ppm. That's it. When the total chlorine amount is 0.1 ppm or more, the shell forming reaction is efficiently performed on the surface of the curing agent, and a shell having excellent storage stability can be obtained.

  In this Embodiment, it can be set as the curable composition containing the said imidazole compound containing microencapsulated composition and an epoxy resin. The curable composition may be used as it is, depending on the application. The curable composition of the present embodiment can exhibit desired performance by being cured by heating.

  The curable composition preferably contains 10 to 50,000 parts by mass of an epoxy resin with respect to 100 parts by mass of the imidazole compound-containing microencapsulated composition. When the epoxy resin is 50,000 parts by mass or less, the curing reactivity tends to be higher, and when it is 10 parts by mass or more, the viscosity of the curable composition does not increase, and better workability is obtained. There is a tendency. From such a viewpoint, the compounding amount of the epoxy resin in the curable composition is more preferably 100 to 5000 parts by mass, and still more preferably 120 to 1000 parts per 100 parts by mass of the imidazole compound-containing microencapsulated composition. It is a mass part, Most preferably, it is 150-400 mass part.

  The curable composition of the present embodiment is preferably mainly composed of an imidazole compound-containing microencapsulated composition and an epoxy resin. The main component here means a component that is 50% by mass or more of the total components, and preferably 60% by mass or more of the thermosetting component. More preferably, it is 70 mass% or more.

  Examples of the component not involved in the curability include an extender, a reinforcing material, a filler, a conductive material, a pigment, an organic solvent, a resin, and the like, and these components are 0 to 90 mass with respect to the entire composition. % Is preferably used.

  Furthermore, in this Embodiment, it can be set as the masterbatch type hardening | curing agent containing the said curable composition. Preferably, it is a masterbatch type hardening | curing agent which has a curable composition as a main component. Here, a main component means that 50 mass% or more is contained in all the components.

  The total chlorine content of the masterbatch type curing agent is preferably 2500 ppm or less, more preferably 1500 ppm or less, still more preferably 800 ppm or less, and still more preferably, in order to achieve both high curability and storage stability. Is not more than 400 ppm, more preferably not more than 200 ppm, still more preferably not more than 100 ppm, still more preferably not more than 80 ppm, and still more preferably not more than 50 ppm.

  The total chlorine content of the epoxy resin in the master batch type curing agent is preferably 2500 ppm or less, more preferably 1500 ppm or less, and still more preferably 800 ppm or less, for achieving both high curability and storage stability. More preferably, it is 100 ppm or less, and still more preferably 50 ppm or less.

  When the epoxy resin in the masterbatch type curing agent is the same as the epoxy resin used in the shell formation reaction, the total chlorine content of the epoxy resin in the masterbatch type curing agent is 0.01 ppm or more from the viewpoint of facilitating the control of the shell formation reaction. Is preferred. More preferably 0.02 ppm or more, still more preferably 0.05 ppm or more, still more preferably 0.1 ppm or more, still more preferably 0.2 ppm or more, and still more preferably 0.5 ppm. That's it.

  A method for producing the masterbatch type curing agent of the present embodiment is not particularly limited, but a method of dispersing an imidazole compound-containing microencapsulated composition in an epoxy resin using, for example, a three-roll roll; A method of obtaining a master batch type curing agent at the same time as performing microencapsulation by performing a coating reaction of the core in a resin can be mentioned. Among these, the latter is preferable because of high productivity.

  You may make the masterbatch type hardening | curing agent of this Embodiment contain boric acid compounds, such as a cyclic borate ester compound. By containing a boric acid compound, the storage stability of the composition, particularly the storage stability at high temperatures can be improved.

  The boric acid compound is preferably a compound in which boron obtained from boric acid and an aliphatic or aromatic diol is contained in a cyclic structure. For example, tris-o-phenylene bisborate, bis-dimethyltrimethylene boroborate, bis-dimethylethylene boroborate, bis-diethylethylene boroborate, 2,2′-oxybis (5,5′-dimethyl-1,3, 2-oxaborinane) and the like. Among these, 2,2'-oxybis (5,5'-dimethyl-1,3,2-oxaborinane) is preferable.

  As content of the said cyclic boric-ester compound, Preferably it is 0.001-10 mass parts with respect to 100 mass parts of epoxy resins in a masterbatch type hardening | curing agent, More preferably, it is 0.01-2 mass parts. Yes, more preferably 0.05 to 0.9 parts by mass. By setting the content in this range, an excellent cured product having excellent storage stability at high temperature of the composition and not impairing short-time curability, heat resistance, adhesiveness, and connection reliability can be obtained. Can do.

  In this Embodiment, the curable composition can contain another component according to various uses in the range which does not reduce the function. The content of other components is usually preferably less than 50% by mass with respect to the total composition.

  The epoxy resin used in the curable composition and the masterbatch type curing agent of the present embodiment may be one having an average of two or more epoxy groups per molecule. For example, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A, etc. Bisphenol type epoxy resin obtained by glycidylation of bisphenols; Epoxy resin obtained by glycidylation of other dihydric phenols such as biphenol, dihydroxynaphthalene and 9,9-bis (4-hydroxyphenyl) fluorene; 1,1,1-tris (4-Hydroxyphenyl) methane, 4,4- (1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol Epoxy resin obtained by glycidylation of trisphenols such as 1, epoxy resin obtained by glycidylation of tetrakisphenol such as 1,1,2,2, -tetrakis (4-hydroxyphenyl) ethane; phenol novolak, cresol novolak, bisphenol A novolak , Novolak epoxy resins obtained by glycidylation of novolaks such as brominated phenol novolak and brominated bisphenol A novolac; epoxy resins obtained by glycidylation of polyhydric phenols; polyhydric alcohols such as glycerin and polyethylene glycol are glycidylated Aliphatic ether type epoxy resins; ether ester type epoxy resins obtained by glycidylation of hydroxycarboxylic acids such as p-oxybenzoic acid and β-oxynaphthoic acid; such as phthalic acid and terephthalic acid Ester-type epoxy resin obtained by glycidylation of polycarboxylic acid; amine-type epoxy resin such as glycidylated products of amine compounds such as 4,4-diaminodiphenylmethane and m-aminophenol, triglycidyl isocyanurate, and 3,4-epoxycyclohexylmethyl And alicyclic epoxides such as −3 ′, 4′-epoxycyclohexanecarboxylate.

  The mixing ratio of the imidazole compound-containing microencapsulated composition of the present embodiment and the epoxy resin is not particularly limited, and can be determined from the viewpoints of curability and a cured product. The content of the epoxy resin with respect to 100 parts by mass of the imidazole compound-containing microencapsulated composition is preferably 0.1 to 1000 parts by mass, more preferably 0.5 to 500 parts by mass, and still more preferably, 3 to 200 parts by mass. By setting the content of the epoxy resin to 1000 parts by mass or less, it is possible to obtain practically satisfactory curing performance, and by setting it to 100 parts by mass or more, each component is not unevenly distributed and has a good balance. Curing performance can be obtained.

  In the masterbatch type curing agent of the present embodiment, a resin generally called a phenoxy resin, which is a high molecular weight epoxy resin and has a self-film forming property, can be mixed.

  The imidazole compound-containing microencapsulated composition, curable composition, and masterbatch type curing agent of the present embodiment are at least one selected from the group consisting of acid anhydrides, phenols, hydrazides, and guanidines. These curing agents can be used in combination.

  Examples of acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, -3-chlorophthalic anhydride, -4-chlorophthalic anhydride, and benzophenone anhydride. Examples thereof include tetracarboxylic acid, succinic anhydride, methyl succinic anhydride, dimethyl succinic anhydride, dichlor succinic anhydride, methyl nadic acid, dodecyl succinic acid, chlorendec succinic anhydride, maleic anhydride and the like.

  Examples of phenols include phenol novolak, cresol novolak, bisphenol A novolak and the like; hydrazines include, for example, succinic acid dihydrazide, adipic acid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide terephthalic acid dihydrazide, p-oxybenzoic acid hydrazide , Salicylic acid hydrazide, phenylaminopropionic acid hydrazide, maleic acid dihydrazide and the like.

  Examples of guanidines include dicyandiamide, methylguanidine, ethylguanidine, propylguanidine, butylguanidine, dimethylguanidine, trimethylguanidine, phenylguanidine, diphenylguanidine, toluylguanidine and the like.

  Preferable curing agents include guanidines and acid anhydrides, and more preferable examples include dicyandiamide, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylnadic acid anhydride.

  When using a hardening | curing agent, it is preferable to use it in the quantity from which a hardening | curing agent will be 1-200 mass parts with respect to 0.01-200 mass parts of imidazole compound containing microencapsulation compositions. By using in this range, the composition which was further excellent in sclerosis | hardenability and storage stability can be given, and the hardened | cured material more excellent in heat resistance and water resistance can be obtained.

  The master batch type curing agent of the present embodiment includes, as desired, a filler, a reinforcing material, a filler, conductive fine particles, a pigment, an organic solvent, a reactive diluent, a non-reactive diluent, other resins, crystals. A basic alcohol, a coupling agent, etc. can be added.

  Examples of the filler include coal tar, glass fiber, asbestos fiber, boron fiber, carbon fiber, cellulose, polyethylene powder, polypropylene powder, quartz powder, mineral silicate, mica, asbestos powder, and slate powder. It is done.

  Examples of the pigment include kaolin, aluminum oxide trihydrate, aluminum hydroxide, chalk powder, gypsum, calcium carbonate, antimony trioxide, penton, silica, aerosol, lithopone, barite, and titanium dioxide.

  Examples of the conductive fine particles include carbon black, graphite, carbon nanotube, fullerene, iron oxide, gold, silver, aluminum powder, iron powder, nano-sized metal crystals, and intermetallic compounds.

  Examples of the organic solvent include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate and the like.

  Examples of the reactive diluent include butyl glycidyl ether, N, N′-glycidyl-o-toluidine, phenyl glycidyl ether, styrene oxide, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and 1,6-hexanediol diester. A glycidyl ether etc. are mentioned.

  Examples of non-reactive diluents include dioctyl phthalate, dibutyl phthalate, dioctyl adipate, and petroleum solvents.

Examples of other resins include modified epoxy resins such as polyester resins, polyurethane resins, acrylic resins, polyether resins, melamine resins, urethane-modified epoxy resins, rubber-modified epoxy resins, and alkyd-modified epoxy resins. Examples of the crystalline alcohol include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, pentaerythritol, sorbitol, sucrose, and trimethylolpropane.
Any of these is effectively used according to the application.

  In the present embodiment, a paste-like composition, a film-like composition, an adhesive, a bonding paste, a bonding film, a conductive material, an anisotropic conductive material containing the curable composition or the masterbatch-type curing agent. Conductive material, insulating material, sealing material, coating material, coating composition, prepreg, heat transfer material, and the like.

  The adhesive, bonding paste, and bonding film are useful as liquid adhesives, film adhesives, die bonding materials, and the like. Examples of the method for producing the film adhesive include the methods described in JP-A-62-141083 and JP-A-05-295329. More specifically, a solid epoxy resin, a liquid epoxy resin, and, if necessary, a solid urethane resin are dissolved, mixed, or dispersed in toluene so that the total amount is 50% by mass with respect to all components including the solvent. Make a solution. A varnish is prepared by adding and dispersing the masterbatch type curing agent of the present embodiment so as to be 30% by mass with respect to the solution. This varnish is applied to, for example, a peeling polyethylene terephthalate substrate having a thickness of 50 μm so as to have a thickness of 30 μm after drying of toluene. By drying toluene, it is possible to obtain a bonding film that is inactive at normal temperature and exhibits adhesiveness by the action of the latent curing agent when heated.

Examples of the conductive material include a conductive film and a conductive paste.
Examples of the anisotropic conductive material include an anisotropic conductive film and an anisotropic conductive paste. Examples of the production method include the method described in JP-A-01-113480. More specifically, for example, in the production of the above-described bonding film, the conductive material and the anisotropic conductive material are mixed and dispersed at the time of preparing the varnish, applied to the substrate for peeling, and then dried. be able to.

  Examples of the conductive particles include solder particles, nickel particles, nano-sized metal crystals, metal particles coated with other metals, metal particles such as copper and silver inclined particles, styrene resin, urethane resin, melamine, and the like. Examples thereof include particles obtained by coating resin particles such as resin, epoxy resin, acrylic resin, phenol resin, and styrene-butadiene resin with a conductive thin film such as gold, nickel, silver, copper, and solder. The conductive particles are usually spherical fine particles of about 1 to 20 μm.

  As a base material in the case of forming a film, for example, there is a method of drying a solvent after coating on a base material such as polyester, polyethylene, polyimide, polytetrafluoroethylene and the like.

  Examples of the insulating material include an insulating adhesive film and an insulating adhesive paste. By using the bonding film described above, an insulating adhesive film that is an insulating material can be obtained. In addition to using a sealing material, an insulating adhesive paste can be obtained by blending an insulating filler among the aforementioned fillers.

  Examples of the sealing material include a solid sealing material, a liquid sealing material, and a film-like sealing material. As a liquid sealing material, it is useful as an underfill material, a potting material, a dam material or the like. As a manufacturing method of the sealing material, for example, methods described in JP-A Nos. 05-43661 and 2002-226675 can be used. By this manufacturing method, a molding material for sealing / impregnation of electric / electronic parts can be obtained. More specifically, after adding a bisphenol A type epoxy resin, a curing agent such as methylhexahydrophthalic anhydride, which is an acid anhydride curing agent, and spherical fused silica powder and mixing them uniformly, the present embodiment A sealing material can be obtained by further adding and uniformly mixing the curable composition or masterbatch type curing agent.

  Examples of the coating material include an electronic material coating material, an overcoat material for a printed wiring board cover, a resin composition for interlayer insulation of a printed circuit board, and an electromagnetic wave absorbing material. Examples of the method for producing the coating material include the methods described in JP-B-4-6116, JP-A-07-304931, JP-A-08-64960, JP-A-2003-246838, and the like. It is done. More specifically, after selecting silica or the like from the filler and blending bisphenol A type epoxy resin, phenoxy resin, rubber-modified epoxy resin, etc. as filler, the curable composition or masterbatch type of the present embodiment A curing agent is blended and a 50% by mass solution is prepared with methyl ethyl ketone (MEK). This is coated on a polyimide film with a thickness of 50 μm, laminated with copper foil at 60 to 150 ° C., and then heated and cured at 180 to 200 ° C., so that the interlayer is coated with an epoxy resin composition. A board can be obtained.

  Examples of the method for producing the coating composition include the methods described in JP-A-11-323247, JP-A-2005-113103, and the like. More specifically, bisphenol A type epoxy resin is blended with titanium dioxide, talc, etc., and a 1: 1 (mass ratio) mixed solvent of methyl isobutyl ketone (MIBK) / xylene is added, stirred and mixed with the main agent. To do. A coating composition can be obtained by adding the curable composition or masterbatch type curing agent of the present embodiment to this and dispersing it uniformly.

  The prepreg is produced by, for example, impregnating a reinforcing base material with an epoxy resin composition and heating it as described in JP-A 09-71633, WO 98/44017, etc. be able to. Examples of the varnish solvent to be impregnated include methyl ethyl ketone, acetone, ethyl cellosolve, methanol, ethanol, isopropyl alcohol and the like, and it is preferable that these solvents do not remain in the prepreg. In addition, the kind of reinforcement base material is not specifically limited, For example, paper, a glass cloth, a glass nonwoven fabric, an aramid cloth, a liquid crystal polymer etc. are mentioned. The ratio of the resin composition and the reinforcing substrate is not particularly limited, but it is usually preferable that the resin content in the prepreg is 20 to 80% by mass.

  Examples of the method for producing the heat conductive material include methods described in JP-A Nos. 06-136244, 10-237410, 2000-3987, and the like. More specifically, an epoxy resin as a thermosetting resin, a phenol novolac curing agent as a curing agent, and graphite powder as a heat conductive filler are blended and uniformly kneaded. A thermally conductive resin paste can be obtained by blending the curable composition or masterbatch type curing agent of the present embodiment into this.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to a following example. “Part” or “%” in Examples and Comparative Examples is based on mass unless otherwise specified. The physical property evaluation test of the resin and its cured product according to this example and the comparative example was performed by the method described below.

(1) Particle size distribution measurement The particle size distribution was measured by a dry method using a laser diffraction particle size distribution measuring device HELOS / BF-M manufactured by Nippon Laser Corporation.

(2) Melting point measurement Using a differential scanning calorimeter DSC-60 manufactured by Shimadzu Corporation, analysis was performed at a heating rate of 10 ° C / min, and the endothermic peak top on the obtained DSC chart was defined as the melting point.

(3) Quantification of low molecular amine compound A high-performance liquid chromatograph (manufactured by Shimadzu Corporation, SCL-10AVP, detector SPD-10AVP; hereinafter, HPLC) was used, and inert silica C4 manufactured by GL Sciences Inc. was used as the column. The mobile phase was methanol / water = 55/50, sodium dodecyl sulfate added to 20 mM, and phosphoric acid added to pH = 3-4. The detection wavelength was 230 nm. The low molecular amine compound content in the fine powdered imidazole compound-containing composition was quantified from the peak area of the low molecular amine compound on the HPLC analysis chart.

(4) FT-IR measurement Absorbance was measured using a Fourier transform infrared spectrophotometer FT / IR-410 manufactured by JASCO Corporation.

(5) Separation of imidazole compound-containing microencapsulated composition from masterbatch type curing agent The masterbatch type curing agent was repeatedly washed and filtered using xylene until the epoxy resin disappeared. Next, washing and filtration with cyclohexane are repeated until the xylene disappears. Cyclohexane was filtered off, and the cyclohexane was completely removed and dried at a temperature of 50 ° C. or lower.

(6) Separation of Capsule Membrane from Imidazole Compound-Containing Microencapsulated Composition The imidazole compound-containing microencapsulated composition is repeatedly washed and filtered with methanol until the curing agent for epoxy resin disappears, and the temperature is 50 ° C. or less. The methanol was completely removed and dried at the temperature.

(7) Curing rate evaluation The gel time on a 140 degreeC and 100 degreeC hotplate was measured.
Gel time is the action of dropping 0.5g of the one-part epoxy resin curable composition produced in the examples or comparative examples on the hot plate and stirring with the bamboo skewer, and separating the bamboo skewer from the composition every few seconds. The time during which the composition no longer pulled into the bamboo skewers was measured as the gel time.

(8) Storage stability evaluation The one-component epoxy resin curable compositions produced in the examples or comparative examples are stored in a constant temperature bath at 40 ° C., and the viscosity change cannot be observed after a certain time, “◎”, viscosity change Can be observed, the fluidity is “◯” and the non-fluidity is “x”.

(9) Solvent stability evaluation A composition prepared by mixing the one-component epoxy resin curable composition prepared in Examples or Comparative Examples and the solvent (toluene, ethyl acetate, and methyl ethyl ketone) at a ratio of 4: 1 was prepared at 40 ° C. Store for 8 hours, 1 week or 2 weeks in a thermostatic bath. “◎” indicates that the viscosity change cannot be observed, “○” indicates that the viscosity change can be observed, but “×” indicates that the fluidity does not flow, and “×” indicates that the fluidity does not flow. It was.

[Example 1]
30.0 g of 1-aminoethyl-2-methylimidazole (239.67 mmol, manufactured by Shikoku Kasei Co., Ltd.) was dissolved in 600 mL of acetonitrile, and 17 mL of 1,6-hexamethylene diisocyanate (105.92 mmol, Wako Pure Chemical Industries, Ltd.) was stirred at room temperature. Kogyo Co., Ltd.) was added dropwise at a rate such that the temperature of the reaction solution did not exceed 45 ° C. A white solid began to form during the addition and became a slurry. After the dropwise addition, the mixture was stirred at room temperature for 3 hours, and the resulting white solid was collected by filtration and dried under reduced pressure to obtain 41.67 g (yield 94%) of an imidazole compound represented by the following formula (6). The obtained imidazole compound was identified by proton nuclear magnetic resonance spectrum and infrared absorption spectrum. Moreover, about the low molecular amine compound which exists with the imidazole compound represented by Formula (6), it quantified by the method of said (3) using HPLC.

The obtained white solid was ground with a mortar to obtain a coarsely pulverized product that was passed through a sieve having an opening of 212 μm. The obtained coarsely pulverized product was pulverized using a jet mill apparatus (Nanojet Mizer NJ-30 type, manufactured by Aisin Nano Technologies Co., Ltd.). A fine powdery imidazole compound was obtained. Fine powder in 200 parts by mass of bisphenol F type epoxy resin (epoxy equivalent 175 g / eq, diol terminal impurity component / basic structure component = 0.13, total chlorine amount 1900 ppm: hereinafter referred to as “epoxy resin (A)”). 100 parts by weight of the imidazole compound, 1 part by weight of water and 7 parts by weight of tolylene diisocyanate were added and the reaction was continued for 3 hours while stirring at 40 ° C. Then, shell formation reaction was performed at 50 degreeC for 6 hours, and the masterbatch type hardening | curing agent was obtained.
The microcapsule imidazole compound-containing microencapsulated composition is separated from the masterbatch type curing agent using xylene, and further the capsule membrane is separated and has bonding groups (x) and (y) by FT-IR measurement. It was confirmed.
Further, 100 parts by mass of bisphenol A type epoxy resin (epoxy equivalent 189 g / eq, total chlorine amount 1200 ppm: hereinafter referred to as epoxy resin (B)) was blended with 30 parts by mass of the obtained master batch type curing agent. The curing speed, storage stability, and solvent stability of the one-component epoxy resin curable composition were evaluated. The obtained results are shown in Table 1.

[Example 2]
1-Aminoethyl-2-methylimidazole 30.0 g (239.67 mmol, manufactured by Shikoku Kasei Co., Ltd.) was dissolved in 600 mL of acetonitrile, and 81 mL (235.74 mmol, manufactured by Wako Pure Chemical Industries, Ltd.) with stirring at room temperature. ) Was added dropwise at a rate such that the temperature of the reaction solution did not exceed 45 ° C. After the dropwise addition, the mixture was stirred at room temperature for 3 hours, and the resulting white solid was collected by filtration and dried under reduced pressure to obtain 93.21 g (yield 94%) of an imidazole compound represented by the following formula (7). The obtained imidazole compound was identified by proton nuclear magnetic resonance spectrum and infrared absorption spectrum. Moreover, about the low molecular amine compound which exists with the imidazole compound represented by Formula (7), it quantified by the method of said (3) using HPLC.

  The obtained white solid was pulverized in the same manner as in Example 1 to obtain a fine powdery imidazole compound having a particle size of 0.1 to 50 μm in a proportion of 100 mass% and a maximum particle size of 13 μm. Further, a masterbatch type epoxy resin curing agent was obtained in the same manner as in Example 1. This was confirmed to have bonding groups (x) and (y) as in Example 1. Further, in the same manner as in Example 1, when 100 parts of the epoxy resin (B) was blended with 30 parts of the obtained masterbatch type epoxy resin curing agent, the curing speed and storage stability of the one-part epoxy resin curable composition were blended. And solvent stability were evaluated. The obtained results are shown in Table 1.

[Example 3]
10.0-aminoethyl-2-methylimidazole (30.0 g, 239.67 mmol, manufactured by Shikoku Kasei Co., Ltd.) was dissolved in 600 mL of acetonitrile, and reacted with 30 mL of cyclohexyl isocyanate (237.28 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) while stirring at room temperature. The liquid temperature was added dropwise at a rate not exceeding 45 ° C. After dropping, the mixture was stirred at room temperature for 3 hours, and the resulting white solid was collected by filtration and dried under reduced pressure to obtain 55.24 g (yield 93%) of an imidazole compound represented by the following formula (8). The obtained imidazole compound was identified by proton nuclear magnetic resonance spectrum and infrared absorption spectrum. Moreover, about the low molecular amine compound which exists with the imidazole compound represented by Formula (8), it quantified by the method of said (3) using HPLC.

  The obtained white solid was pulverized in the same manner as in Example 1 to obtain a fine powdery imidazole compound having a particle size of 0.1 to 50 μm in a proportion of 100 mass% and a maximum particle size of 14 μm. Further, a masterbatch type epoxy resin curing agent was obtained in the same manner as in Example 1. This was confirmed to have bonding groups (x) and (y) as in Example 1. Further, in the same manner as in Example 1, when 100 parts of the epoxy resin (B) was blended with 30 parts of the obtained masterbatch type epoxy resin curing agent, the curing speed and storage stability of the one-part epoxy resin curable composition were blended. And solvent stability were evaluated. The obtained results are shown in Table 1.

[Example 4]
10.0-aminopropyl-2-methylimidazole (30.0 g, 215.52 mmol, manufactured by Shikoku Kasei Co., Ltd.) was dissolved in 600 mL of acetonitrile, and 51 mL of n-dodecyl isocyanate (209.95 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) with stirring at room temperature. Was added dropwise at a rate such that the temperature of the reaction solution did not exceed 45 ° C. After dropping, the mixture was stirred at room temperature for 3 hours, and the produced white solid was collected by filtration and dried under reduced pressure to obtain 69.18 g (yield 94%) of an imidazole compound represented by the following formula (9). The obtained imidazole compound was identified by proton nuclear magnetic resonance spectrum and infrared absorption spectrum. Moreover, about the low molecular weight amine compound which exists with the imidazole compound represented by Formula (9), it quantified by the method of said (3) using HPLC.

  The obtained white solid was pulverized in the same manner as in Example 1 to obtain a fine powdery imidazole compound having a particle size of 0.1 to 50 μm in a proportion of 100 mass% and a maximum particle size of 13 μm. Further, a master batch type curing agent was obtained in the same manner as in Example 1. Also about this, it was confirmed that it has bonding groups (x) and (y) as in Example 1. Further, in the same manner as in Example 1, when 100 parts by mass of the epoxy resin (B) is blended with 30 parts by mass of the obtained master batch type curing agent, the curing rate and storage stability of the one-component epoxy resin curable composition The solvent stability was evaluated. The obtained results are shown in Table 1.

[Example 5]
10.0 aminopropyl-2-methylimidazole (30.0 g, 215.52 mmol, manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 600 mL of acetonitrile, and 73 mL (212.52 mmol, Wako Pure Chemical Industries, Ltd.) of n-octadecyl isocyanate was stirred at room temperature. Was added dropwise at a rate such that the temperature of the reaction solution did not exceed 45 ° C. After dropping, the mixture was stirred at room temperature for 3 hours and concentrated under reduced pressure. The resulting white solid was collected by filtration and dried under reduced pressure to obtain 86.81 g of imidazole compound represented by the following formula (10) (yield 94%). Obtained. The obtained imidazole compound was identified by proton nuclear magnetic resonance spectrum and infrared absorption spectrum. Moreover, about the low molecular amine compound which exists with the imidazole compound represented by Formula (10), it quantified by the method of said (3) using HPLC.

  The obtained white solid was pulverized in the same manner as in Example 1 to obtain a fine powdery imidazole compound having a particle size of 0.1 to 50 μm in a proportion of 100 mass% and a maximum particle size of 13 μm. Further, a master batch type curing agent was obtained in the same manner as in Example 1. This was confirmed to have bonding groups (x) and (y) as in Example 1. Further, in the same manner as in Example 1, when 100 parts by mass of the epoxy resin (B) is blended with 30 parts by mass of the obtained master batch type curing agent, the curing rate and storage stability of the one-component epoxy resin curable composition The solvent stability was evaluated. The obtained results are shown in Table 1.

[Example 6]
10.0-aminopropyl-2-methylimidazole (30.0 g, 215.52 mmol, manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in acetonitrile (600 mL) and stirred at room temperature with 26 mL of cyclohexyl isocyanate (205.64 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.). Was added dropwise at a rate such that the temperature of the reaction solution did not exceed 45 ° C. After the dropwise addition, the mixture was stirred at room temperature for 3 hours, and the resulting white solid was collected by filtration and dried under reduced pressure to obtain 48.38 g (yield 89%) of an imidazole compound represented by the following formula (11). The obtained imidazole compound was identified by proton nuclear magnetic resonance spectrum and infrared absorption spectrum. Moreover, about the low molecular weight amine compound which exists with the imidazole compound represented by Formula (11), it quantified by the method of said (3) using HPLC.

  The obtained white solid was pulverized in the same manner as in Example 1 to obtain a fine powdery imidazole compound having a particle size of 0.1 to 50 μm in a proportion of 100 mass% and a maximum particle size of 17 μm. Further, a master batch type curing agent was obtained in the same manner as in Example 1. This was confirmed to have bonding groups (x) and (y) as in Example 1. Further, in the same manner as in Example 1, when 100 parts by mass of the epoxy resin (B) is blended with 30 parts by mass of the obtained master batch type curing agent, the curing rate and storage stability of the one-component epoxy resin curable composition The solvent stability was evaluated. The obtained results are shown in Table 1.

[Example 7]
10.0 aminopropyl-2-methylimidazole (30.0 g, 215.52 mmol, manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 600 mL of acetonitrile, and 17 mL of 1,6-hexamethylene diisocyanate (105.92 mmol, Japanese) was stirred at room temperature. (Manufactured by Kojun Pharmaceutical Co., Ltd.) was added dropwise at a rate such that the temperature of the reaction solution did not exceed 45 ° C. After the dropwise addition, the mixture was stirred at room temperature for 3 hours, and the resulting white solid was collected by filtration and dried under reduced pressure to obtain 43.99 g (yield 93%) of an imidazole compound represented by the following formula (12). The obtained imidazole compound was identified by proton nuclear magnetic resonance spectrum and infrared absorption spectrum. Moreover, about the low molecular amine compound which exists with the imidazole compound represented by Formula (12), it quantified by the method of said (3) using HPLC.

  The obtained white solid was pulverized in the same manner as in Example 1 to obtain a fine powdery imidazole compound having a particle size of 0.1 to 50 μm in a proportion of 100 mass% and a maximum particle size of 12 μm. Further, a master batch type curing agent was obtained in the same manner as in Example 1. This was confirmed to have bonding groups (x) and (y) as in Example 1. Further, in the same manner as in Example 1, when 100 parts by mass of the epoxy resin (B) is blended with 30 parts by mass of the obtained master batch type curing agent, the curing rate and storage stability of the one-component epoxy resin curable composition The solvent stability was evaluated. The obtained results are shown in Table 1.

[Example 8]
1-Aminopropyl-2-methylimidazole 30.0 g (215.52 mmol, manufactured by Shikoku Kasei Co., Ltd.) was dissolved in 600 mL of acetonitrile, and 16 mL of m-xylylene diisocyanate (102.02 mmol, Tokyo Chemical Industry Co., Ltd.) was stirred at room temperature. Product) was added dropwise at a rate such that the temperature of the reaction solution did not exceed 45 ° C. After the dropwise addition, the mixture was stirred at room temperature for 3 hours, and the produced white solid was collected by filtration and dried under reduced pressure to obtain 44.27 g (yield 93%) of an imidazole compound represented by the following formula (13). The obtained imidazole compound was identified by proton nuclear magnetic resonance spectrum and infrared absorption spectrum. Moreover, about the low molecular amine compound which exists with the imidazole compound represented by Formula (13), it quantified by the method of said (3) using HPLC.

  The obtained white solid was pulverized in the same manner as in Example 1 to obtain a fine powdery imidazole compound having a particle size of 0.1 to 50 μm in a proportion of 100 mass% and a maximum particle size of 12 μm. Further, a master batch type curing agent was obtained in the same manner as in Example 1. This was confirmed to have bonding groups (x) and (y) as in Example 1. Further, in the same manner as in Example 1, when 100 parts by mass of the epoxy resin (B) is blended with 30 parts by mass of the obtained master batch type curing agent, the curing rate and storage stability of the one-component epoxy resin curable composition The solvent stability was evaluated. The obtained results are shown in Table 1.

[Example 9]
In Example 5, a shell forming reaction was performed in the same manner except that 2.5 parts by mass of glycerin was used instead of 1 part by mass of water to obtain a master batch type curing agent. About this, it confirmed that it had a coupling group (x), (y), (z) by the FT-IR measurement similarly to the Example and 1. Furthermore, the curing rate and storage stability of the one-component epoxy resin curable composition when 30 parts by mass of the masterbatch type curing agent obtained in 100 parts by mass of the epoxy resin (B) was blended as in Example 1. The solvent stability was evaluated. The obtained results are shown in Table 1.

[Example 10]
Methacrylonitrile 67.09 g (5 mol, manufactured by Wako Pure Chemical Industries, Ltd.) and sodium ethoxide 0.68 g (0.01 mol, manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 1500 mL of N, N-dimethylformamide and 100 ° C. While stirring, 82.10 g of 2-methylimidazole (1 mol, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, and the mixture was stirred for 4 hours after the dropwise addition. The obtained reaction solution was purified by distillation under reduced pressure to obtain 1- (2-cyanopropyl) -2-methylimidazole represented by the following formula (14). Next, 74.60 g (0.5 mol) of 1- (2-cyanopropyl) -2-methylimidazole was added to the autoclave, 200 g of 2-propanol as a solvent, and a developed cobalt catalyst (ODHT-60, manufactured by Kawaken Fine Chemical Co., Ltd.). 15g was charged. Next, the hydrogen pressure in the reactor was 3.92 MPa, and the reaction was performed at 100 ° C. for 3 hours. After the reaction, the catalyst was filtered off by suction filtration, and then the reaction solution was purified by distillation under reduced pressure to obtain 1- (1-amino-2-methylpropyl) -2-methylimidazole represented by the following formula (15). . Next, 30.0 g (196 mmol) of 1- (1-amino-2-methylpropyl) -2-methylimidazole was dissolved in 600 mL of acetonitrile, and 57.3 g (194 mmol, Wako Pure Chemical Industries, Ltd.) of n-octadecyl isocyanate was stirred at room temperature. Kogyo Co., Ltd.) was added dropwise at a rate such that the temperature of the reaction solution did not exceed 45 ° C. After the dropwise addition, the mixture was stirred at room temperature for 3 hours, and the produced white solid was collected by filtration and dried under reduced pressure to obtain 78.30 g (yield 90%) of an imidazole compound represented by the following formula (16). The obtained imidazole compound was identified by proton nuclear magnetic resonance spectrum and infrared absorption spectrum.

  The obtained white solid was pulverized in the same manner as in Example 1 to obtain a fine powdery imidazole compound having a particle size of 0.1 to 50 μm in a proportion of 100 mass% and a maximum particle size of 15 μm. Further, a master batch type curing agent was obtained in the same manner as in Example 1. This was confirmed to have bonding groups (x) and (y) as in Example 1. Furthermore, the curing rate, storage stability, and solvent stability of the one-component epoxy resin curable composition were evaluated when 30 parts by mass of the obtained masterbatch type curing agent was blended with 100 parts by mass of the epoxy resin (B). did. The obtained results are shown in Table 1.

[Example 11]
Allyl cyanide 67.09 g (5 mol, manufactured by Wako Pure Chemical Industries, Ltd.) and sodium ethoxide 0.68 g (0.01 mol, manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 1500 mL of N, N-dimethylformamide and stirred at 100 ° C. Then, 82.10 g (1 mol, manufactured by Wako Pure Chemical Industries, Ltd.) of 2-methylimidazole was dropped, and the mixture was stirred for 2 hours after dropping. The obtained reaction solution was purified by distillation under reduced pressure to obtain 1-cyanopropyl-2-methylimidazole represented by the following formula (17). Subsequently, 74.60 g (0.5 mol) of 1-cyanopropyl-2-methylimidazole, 200 g of 2-propanol as a solvent, and 15 g of a developed cobalt catalyst (ODHT-60, manufactured by Kawaken Fine Chemical Co., Ltd.) were charged into the autoclave. Next, the hydrogen pressure in the reactor was 3.92 MPa, and the reaction was performed at 100 ° C. for 3 hours. After the reaction, the catalyst was filtered off by suction filtration, and then the reaction solution was purified by distillation under reduced pressure to obtain 1-aminobutyl-2-methylimidazole represented by the following formula (18). Next, 30.0 g (196 mmol) of 1-aminobutyl-2-methylimidazole was dissolved in 600 mL of acetonitrile, and 57.3 g (194 mmol, manufactured by Wako Pure Chemical Industries, Ltd.) of n-octadecyl isocyanate was added to the reaction solution while stirring at room temperature. The temperature was dropped at a rate not exceeding 45 ° C. After dropping, the mixture was stirred at room temperature for 3 hours, and the resulting white solid was collected by filtration and dried under reduced pressure to obtain 75.30 g (yield 86%) of an imidazole compound represented by the following formula (19). The obtained imidazole compound was identified by proton nuclear magnetic resonance spectrum and infrared absorption spectrum.

  The obtained white solid was pulverized in the same manner as in Example 1 to obtain a fine powdery imidazole compound having a particle size of 0.1 to 50 μm in a proportion of 100 mass% and a maximum particle size of 14 μm. Further, a master batch type curing agent was obtained in the same manner as in Example 1. This was confirmed to have bonding groups (x) and (y) as in Example 1. Furthermore, the curing rate, storage stability, and solvent stability of the one-component epoxy resin curable composition were evaluated when 30 parts by mass of the obtained masterbatch type curing agent was blended with 100 parts by mass of the epoxy resin (B). did. The obtained results are shown in Table 1.

[Comparative Example 1]
One liquid when 100 parts by mass of the finely powdered imidazole compound represented by the formula (7) obtained in Example 2 is blended with 200 parts by mass of the epoxy resin (A) and 1000 parts by mass of the epoxy resin (B). The curing rate, storage stability, and solvent stability of the curable epoxy resin curable composition were evaluated. The obtained results are shown in Table 2.

[Comparative Example 2]
19.0 g of bisphenol A type epoxy resin (product name “AER-2603” manufactured by Asahi Kasei Chemicals) and 11.0 g of 2-ethyl-4-methylimidazole (product name “2E4MZ” manufactured by Shikoku Kasei Kogyo Co., Ltd.) are added to 20 mL of methyl ethyl ketone. After dissolution, the reaction was heated to obtain a solid amine adduct at 25 ° C. 100 parts by mass of this amine adduct is melted, 2.5 parts by mass of 2-ethyl-4-methylimidazole is uniformly mixed therein, cooled to room temperature, and ground in the same manner as in Example 1 to obtain a master batch type curing. An agent was obtained. This was confirmed to have bonding groups (x), (y), and (z) as in Example 1. Furthermore, the curing rate of one-component epoxy resin curable composition when the masterbatch type curing agent obtained in 100 parts by mass of the epoxy resin (B) is blended in the same manner as in Example 1, the storage stability, Solvent stability was evaluated. The obtained results are shown in Table 2.

[Preparation of conductive film]
15 parts by mass of bisphenol A type epoxy resin (product name “AER-2603” manufactured by Asahi Kasei Chemicals), 6 parts by mass of phenol novolac resin (product name “BRG-558” manufactured by Showa Polymer Co., Ltd.), synthetic rubber (Nippon Zeon Corporation) 4 parts by mass, manufactured by trade name “Nipol 1072”, weight average molecular weight 300,000) were dissolved in 20 parts by mass of a 1: 1 (mass ratio) mixed solvent of methyl ethyl ketone and butyl cellosolve acetate. In this solution, 74 parts by mass of silver powder was mixed and further kneaded by a three-roll. To this, 30 parts by mass of the master batch type curing agent obtained in Example 7 was further added and mixed uniformly to obtain a conductive adhesive. Using the obtained conductive adhesive, it was cast on a polypropylene film having a thickness of 40 μm and dried and semi-cured at 80 ° C. for 60 minutes to obtain a conductive film having a conductive adhesive layer having a thickness of 35 μm. . Using this conductive film, the conductive adhesive layer was transferred to the conductive film on the back surface of the silicon wafer on a heat block at 80 ° C. Furthermore, when the silicon wafer was fully diced and a semiconductor chip with a conductive adhesive was bonded and cured to the lead frame on a heat block at 200 ° C. for 2 minutes, there was no problem of chip conductivity.

[Preparation of conductive paste]
100 parts by mass of epoxy resin (epoxy equivalent 189 g / eq, total chlorine amount 1200 ppm: hereinafter referred to as “epoxy resin (C)”), 30 parts by mass of the master batch type curing agent obtained in Example 7, average 150 g of flaky silver powder with a particle size of 14 μm and an aspect ratio of 11 (manufactured by Tokuru Chemical Laboratory Co., Ltd.), and a flaky nickel powder with an average particle size of 10 μm and an aspect ratio of 9 (manufactured by High Purity Chemical Co., Ltd.) Name “NI110104”) 60 g was added, stirred until uniform, and then uniformly dispersed with three rolls to obtain a conductive paste. The obtained conductive paste was screen-printed on a polyimide film substrate having a thickness of 1.4 mm, and then heat-cured at 200 ° C. for 1 hour. As a result of measuring the conductivity of the obtained wiring board, it was useful as a conductive paste.

[Production of anisotropic conductive film]
40 parts by mass of bisphenol A type epoxy resin (Asahi Kasei Chemicals, trade name “AER6097”, epoxy equivalent 42500 g / eq) and 30 parts by weight of phenoxy resin (trade name “YP-50”, manufactured by Tohto Kasei) are added to 30 parts of ethyl acetate. Dissolve it, add 30 parts by mass of the masterbatch type curing agent obtained in Example 1 and 5 parts by mass of conductive particles (cross-linked polystyrene plated with gold) with a particle size of 8 μm, and mix uniformly. An epoxy resin composition was obtained. This was applied onto a polyester film, and ethyl acetate was removed by drying at 70 ° C. to obtain an anisotropic conductive film.
The obtained anisotropic conductive film was sandwiched between the IC chip and the electrode and subjected to thermocompression bonding at 30 kg / cm ² for 20 seconds on a 200 ° C. hot plate. It was useful as a conductive material.

[Production of anisotropic conductive paste]
Bisphenol A type epoxy resin (Asahi Kasei Chemicals, trade name “AER6091”, epoxy equivalent 480 g / eq) 50 parts by mass, Bisphenol A type epoxy resin (Asahi Kasei Chemicals, trade name “AER2603”) 50 parts by mass and conductive particles “ After mixing 5 parts by mass of Micropearl Au-205 "(manufactured by Sekisui Chemical Co., Ltd., specific gravity 2.67), 30 parts by mass of the masterbatch type curing agent obtained in Example 7 was added and mixed more uniformly. A conductive paste was obtained. The obtained anisotropic conductive paste was applied on a low alkali glass having an ITO electrode. A ceramic tool at 230 ° C. was pressed and bonded to a test TAB (Tape Automated Bonding) film at a pressure of 2 MPa for 30 seconds. When the resistance value between the adjacent ITO electrodes was measured, it was useful as an anisotropic conductive paste.

[Preparation of insulating paste]
100 parts by mass of bisphenol F type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., trade name “YL983U”), 4 parts by mass of dicyandiamide, 100 parts by mass of silica powder, 10 parts by mass of phenylglycidyl ether as a diluent, and organic phosphorus After sufficiently mixing 1 part by mass of an acid ester (manufactured by Nippon Kayaku Co., Ltd., trade name “PM-2”), the mixture is further kneaded with three rolls. Furthermore, 30 parts by mass of the masterbatch type curing agent obtained in Example 7 was added thereto, and further uniformly mixed, and vacuum degassing and centrifugal defoaming were performed to produce an insulating paste. Using the obtained insulating paste, a semiconductor chip was bonded to a resin substrate by heating and curing at 200 ° C. for 1 hour, and it was useful as an insulating paste.

[Preparation of insulating film]
180 parts by mass of phenoxy resin (manufactured by Toto Kasei Co., Ltd., trade name “YP-50”), cresol novolac type epoxy resin (epoxy equivalent 200 g / eq, product of Nippon Kayaku Co., Ltd., trade name “EOCN-1020-80”) ] 40 parts by weight, spherical silica (average particle size: 2 μm, manufactured by Admatech Co., Ltd., trade name “SE-5101”), 300 parts by weight, and 200 parts by weight of methyl ethyl ketone were prepared and uniformly dispersed. 250 parts by mass of the master batch type curing agent obtained in 7 is added and further stirred and mixed to obtain a solution containing the epoxy resin composition. The obtained solution is applied onto polyethylene terephthalate that has been subjected to mold release treatment so that the thickness after drying is 50 μm, and is dried by heating in a hot-air circulating dryer to provide insulating properties for semiconductor adhesion. A film was obtained. The obtained insulating film for adhering semiconductors is cut together with the supporting substrate larger than the wafer size of 5 inches, and the resin film is aligned with the electrode part side of the wafer with bump electrodes. Next, a support substrate with a release treatment is sandwiched between them, and heat-pressed in vacuum at 70 ° C., 1 MPa, and a pressurization time of 10 seconds to obtain a wafer with an adhesive resin. Subsequently, it was observed that there was no resin peeling of the individual semiconductor element with an adhesive film cut and separated using a dicing saw (manufactured by DISCO, DAD-2H6M) at a spindle rotation speed of 30,000 rpm and a cutting speed of 20 mm / sec. The obtained film was useful as an insulating film.

[Preparation of sealing material]
Bisphenol A type epoxy resin (Asahi Kasei Chemicals, trade name “AER6091”, epoxy equivalent 480 g / eq) 50 parts by mass, Bisphenol A type epoxy resin (Asahi Kasei Chemicals, trade name “AER2603”) 50 parts by mass, anhydrous as curing agent 40 parts by mass of “HN-2200” (manufactured by Hitachi Chemical Co., Ltd.) mainly composed of phthalic acid and 80 parts by mass of spherical fused silica having an average particle diameter of 16 μm were uniformly dispersed and blended. 5 parts by mass of the master batch type curing agent obtained in Example 7 was added thereto to obtain an epoxy resin composition. The obtained epoxy resin composition was applied to a printed wiring board in a 1 cm square so as to have a thickness of 60 μm, and was semi-cured by heating in an oven at 110 ° C. for 10 minutes. After that, a 370 μm thick, 1 cm square silicon chip was placed on a semi-cured epoxy resin composition, and a full curing process was performed at 220 ° C. for 1 hour while applying and applying a load to contact and hold the bump and chip electrodes. went. The obtained sealing material comprising the epoxy resin composition was useful without any problem in appearance and chip conduction.

[Production of coating material]
30 parts by mass of epoxy resin (C), 30 parts by mass of phenoxy resin (trade name “YP-50”, manufactured by Toto Kasei), and methyl ethyl ketone solution of methoxy group-containing silane-modified epoxy resin (manufactured by Arakawa Chemical Industries, Ltd., trade name) 30 parts by weight of the master batch type curing agent obtained in Example 1 was added to 50 parts by weight of “Composeran E103”), and a solution diluted to 50% by weight with methyl ethyl ketone was prepared. The prepared solution was applied onto a peeled PET (polyethylene terephthalate) film (manufactured by Panac Co., Ltd., trade name “SG-1”) using a roll coater, dried and cured at 150 ° C. for 15 minutes, and peeled off. A semi-cured resin (dry film) film thickness of 100 μm was prepared. These dry films were heat-pressed on the above copper-clad laminate at 120 ° C. for 10 minutes at 6 MPa, then returned to room temperature to remove the release film and cured at 200 ° C. for 2 hours. A useful coating material was obtained.

[Preparation of coating composition]
50 parts by mass of bisphenol A type epoxy resin (trade name “AER6091” manufactured by Asahi Kasei Chemicals, epoxy equivalent 480 g / eq), 30 parts by mass of titanium dioxide and 70 parts by mass of talc are blended, and methyl isobutyl ketone (MIBK) is used as a mixed solvent. 140 parts by mass of a 1: 1 (mass ratio) mixed solvent of / xylene was added, stirred and mixed to obtain a main agent. To this, 30 parts by mass of the master batch type curing agent obtained in Example 7 was added and dispersed uniformly to obtain a useful epoxy coating composition.

[Preparation of prepreg]
In a flask in an oil bath at 130 ° C., 15 parts by mass of a novolac type epoxy resin (manufactured by Dainippon Ink and Chemicals, trade name “EPICLON N-740”), bisphenol F type epoxy resin (made by JER, trade name “Epicoat 4005”) 40 parts by mass and 30 parts by mass of bisphenol A type liquid epoxy resin (trade name “AER2603” manufactured by Asahi Kasei Chemicals) are dissolved and mixed, and cooled to 80 ° C. Further, 15 parts by mass of the master batch type curing agent obtained in Example 7 is added, and the mixture is sufficiently stirred and mixed. The resin composition cooled to room temperature was applied onto a release paper with a resin basis weight of 162 g / m ² using a doctor knife to obtain a resin film. Next, a CF cloth made by Mitsubishi Rayon (model number: TR3110, weight per unit area: 200 g / m ² ) obtained by plain weaving carbon fiber having a modulus of elasticity of 24 ton / mm ² at 12.5 pieces / inch is stacked on the resin film to obtain a resin composition. After impregnating the carbon fiber cloth, a polypropylene film was stacked and passed between a pair of rolls having a surface temperature of 90 ° C. to prepare a cloth prepreg. The resin content was 45% by mass. The obtained prepreg is further laminated with the fiber direction aligned, and molded under a curing condition of 150 ° C. for 1 hour to obtain an FRP molded body using carbon fibers as reinforcing fibers. The produced prepreg is useful. Met.

[Preparation of thermally conductive epoxy resin composition]
100% by mass of bisphenol A type epoxy resin (product name “AER2603” manufactured by Asahi Kasei Chemicals), 50% methyl ethyl ketone solution of phenol novolac resin (product name “Tamanor 759” manufactured by Arakawa Chemical Industries, Ltd.) as a curing agent for epoxy resin 40 parts by mass and 15 parts by mass of scaly graphite powder (trade name “HOPG”, manufactured by Union Carbide Co., Ltd.) were stirred until uniform, and then uniformly dispersed by three rolls. To this was added 15 parts by mass of the master batch type curing agent obtained in Example 7, and the mixture was sufficiently stirred and mixed. The obtained conductive paste was used to mount a semiconductor chip (1.5 mm square, thickness 0.8 mm) on a Cu lead frame, and heat cured at 150 ° C. for 30 minutes to obtain an evaluation sample. The thermal conductivity of the obtained sample was measured by a laser flash method. That is, when the thermal conductivity K was determined from the measured thermal diffusivity α, specific heat Cp, and density σ from the following equation, K = α × Cp × σ, K was 5 × 10 ⁻³ Cal / cm · sec · The temperature was not lower than ° C. and was useful as a heat conductive paste.

  It was confirmed that each of the master batch type curing agents of Examples 1 to 11 was excellent in low-temperature curability and excellent in storage stability and solvent stability. Furthermore, it was confirmed that when Q is a hydrocarbon having 3 or more carbon atoms, the melting point is lower and the curing rate at 100 ° C. is faster than when Q has 2 carbon atoms. On the other hand, Comparative Examples 1 and 2 were poor in at least one of low-temperature curability, storage stability, and solvent stability.

  Furthermore, by using the masterbatch type curing agent of Example, conductive film, conductive paste, anisotropic conductive film, anisotropic conductive paste, insulating paste, insulating film, sealing material, coating material, It was confirmed that what is useful as a coating composition, a prepreg, and a thermally conductive epoxy resin composition can be obtained.

  This application is based on a Japanese patent application (Japanese Patent Application No. 2009-106289) filed with the Japan Patent Office on April 24, 2009, the contents of which are incorporated herein by reference.

  The imidazole compound-containing microencapsulated composition of the present invention includes a curable composition, a masterbatch type curing agent, a paste-like composition, a film-like composition, an adhesive, a joining paste, a joining film, and a conductive material. It can be used as various materials including anisotropic conductive materials, insulating materials, sealing materials, coating materials, paint compositions, prepregs, heat conductive materials and the like.

Claims (24)

A core containing an imidazole compound represented by the following formula (1);
A shell containing an organic polymer, an inorganic compound, or both, and covering the surface of the core;
A microencapsulated composition containing an imidazole compound.

(In the formula, R ¹ , R ² and R ³ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. 20 represents a divalent hydrocarbon of 20. m represents an integer of 1 to 3. Z represents an organic group having a valence m, and the organic group includes an oxygen atom, a nitrogen atom, or a phosphorus atom. Which may be a hydrocarbon group or an aromatic group, Y represents a urea bond.)   The imidazole compound-containing microencapsulated composition according to claim 1, wherein the imidazole compound is solid at 10 ° C or higher and is crystalline or amorphous.   The imidazole compound-containing microencapsulated composition according to claim 1 or 2, wherein the imidazole compound is a crystalline solid that is solid at 25 ° C or higher and has a melting point at 250 ° C or lower. The maximum particle size of the imidazole compound is 100 µm or less, and particles having a particle size of 0.1 µm or more and 100 µm or less are contained in the imidazole compound by 90 mass% or more. Item 4. An imidazole compound-containing microencapsulated composition according to Item. The imidazole compound-containing microencapsulated composition according to any one of claims 1 to 4, wherein the core contains the imidazole compound and a low molecular amine compound having a molecular weight of 2000 or less . Said shell, and a biuret bond group that absorbs infrared urea bond group and 1680～1725Cm ^-1 which contains an organic polymer derived from an isocyanate compound as a main component, and absorbs infrared 1630～1680Cm ^-1 The imidazole compound-containing microencapsulated composition according to any one of claims 1 to 5, which is at least on the surface. The said shell contains the organic polymer induced | guided | derived from an isocyanate compound as a main component, and has at least the urethane bond group which absorbs the infrared rays of 1730-1755 cm < ^-1 >, It is any one of Claims 1-6. An imidazole compound-containing microencapsulated composition.   The imidazole compound-containing microencapsulated composition according to any one of claims 1 to 7, wherein the shell is 0.01 to 100 parts by mass with respect to 100 parts by mass of the core.   The curable composition containing 10-50,000 mass parts of epoxy resins with respect to 100 mass parts of imidazole compound containing microencapsulation compositions as described in any one of Claims 1-8.   A master batch type curing agent comprising the curable composition according to claim 9 as a main component.   The paste-like composition containing the curable composition of Claim 9, or the masterbatch type hardening | curing agent of Claim 10.   The curable composition of Claim 9, or the film-form composition containing the masterbatch type hardening | curing agent of Claim 10.   The adhesive containing the curable composition of Claim 9, or the masterbatch type hardening | curing agent of Claim 10.   A joining paste containing the curable composition according to claim 9 or the masterbatch type curing agent according to claim 10.   The film for joining containing the curable composition of Claim 9, or the masterbatch type hardening | curing agent of Claim 10.   The electroconductive material containing the curable composition of Claim 9, or the masterbatch type hardening | curing agent of Claim 10.   An anisotropic conductive material containing the curable composition according to claim 9 or the masterbatch type curing agent according to claim 10.   An anisotropic conductive film containing the curable composition according to claim 9 or the masterbatch type curing agent according to claim 10.   The insulating material containing the curable composition of Claim 9, or the masterbatch type hardening | curing agent of Claim 10.   The sealing material containing the curable composition of Claim 9, or the masterbatch type hardening | curing agent of Claim 10.   Coating material containing the curable composition of Claim 9, or the masterbatch type hardening | curing agent of Claim 10.   The curable composition of Claim 9, or the coating composition containing the masterbatch type hardening | curing agent of Claim 10.   A prepreg containing the curable composition according to claim 9 or the masterbatch-type curing agent according to claim 10.   The heat conductive material containing the curable composition of Claim 9, or the masterbatch type hardening | curing agent of Claim 10.